bluuebunny/crossref_metadata_2025 huggingface dataset:
Evaluation of the volatility basis-set approach for the simulation of organic aerosol formation in the Mexico City metropolitan area
Authors: Tsimpidi A. P. , Karydis V. A. , Zavala M. , Lei W. , Molina L. , Ulbrich I. M. , Jimenez J. L. , Pandis S. N.
Published: April 2010

Abstract. New primary and secondary organic aerosol modules have been added to PMCAMx, a three dimensional chemical transport model (CTM), for use with the SAPRC99 chemistry mechanism based on recent smog chamber studies. The new modelling framework is based on the volatility basis-set approach: both primary and secondary organic components are assumed to be semivolatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. This new framework with the use of the new volatility basis parameters for low-NOx and high-NOx conditions tends to predict 4–6 times higher anthropogenic SOA concentrations than those predicted with the older generation of models. The resulting PMCAMx-2008 was applied in Mexico City Metropolitan Area (MCMA) for approximately a week during April 2003 during a period of very low regional biomass burning impact. The emission inventory, which uses as a starting point the MCMA 2004 official inventory, is modified and the primary organic aerosol (POA) emissions are distributed by volatility based on dilution experiments. The predicted organic aerosol (OA) concentrations peak in the center of Mexico City, reaching values above 40 μg m−3. The model predictions are compared with the results of the Positive Matrix Factorization (PMF) analysis of the Aerosol Mass Spectrometry (AMS) observations. The model reproduces both Hydrocarbon-like Organic Aerosol (HOA) and Oxygenated Organic Aerosol (OOA) concentrations and diurnal profiles. The small OA underprediction during the rush-hour periods and overprediction in the afternoon suggest potential improvements to the description of fresh primary organic emissions and the formation of the oxygenated organic aerosols, respectively, although they may also be due to errors in the simulation of dispersion and vertical mixing. However, the AMS OOA data are not specific enough to prove that the model reproduces the organic aerosol observations for the right reasons. Other combinations of contributions of primary and secondary organic aerosol production rates may lead to similar results. The model results strongly suggest that, during the simulated period, transport of OA from outside the city was a significant contributor to the observed OA levels. Future simulations should use a larger domain in order to test whether the regional OA can be predicted with current SOA parameterizations. Sensitivity tests indicate that the predicted OA concentration is especially sensitive to the volatility distribution of the emissions in the lower volatility bins.
Carbonyl sulfide exchange in a temperate loblolly pine forest grown under ambient and elevated CO2
Authors: White M. L. , Zhou Y. , Russo R. S. , Mao H. , Talbot R. , Varner R. K. , Sive B. C.
Published: April 2010

Abstract. Vegetation, soil and ecosystem level carbonyl sulfide (COS) exchange was observed at Duke Forest, a temperate loblolly pine forest, grown under ambient (Ring 1, R1) and elevated (Ring 2, R2) CO2. During calm meteorological conditions, ambient COS mixing ratios at the top of the forest canopy followed a distinct diurnal pattern in both CO2 growth regimes, with maximum COS mixing ratios during the day (R1=380±4 pptv and R2=373±3 pptv, daytime mean ± standard error) and minimums at night (R1=340±6 pptv and R2=346±5 pptv, nighttime mean ± standard error) reflecting a significant nighttime sink. Nocturnal vegetative uptake (−11 to −21 pmol m−2s−1, negative values indicate uptake from the atmosphere) dominated nighttime net ecosystem COS flux estimates (−10 to −30 pmol m−2s−1) in both CO2 regimes. In comparison, soil uptake (−0.8 to −1.7 pmol m−2 s−1) was a minor component of net ecosystem COS flux. In both CO2 regimes, loblolly pine trees exhibited substantial COS consumption overnight (50% of daytime rates) that was independent of CO2 assimilation. This suggests current estimates of the global vegetative COS sink, which assume that COS and CO2 are consumed simultaneously, may need to be reevaluated. Ambient COS mixing ratios, species specific diurnal patterns of stomatal conductance, temperature and canopy position were the major factors influencing the vegetative COS flux at the branch level. While variability in branch level vegetative COS consumption measurements in ambient and enhanced CO2 environments could not be attributed to CO2 enrichment effects, estimates of net ecosystem COS flux based on ambient canopy mixing ratio measurements suggest less nighttime uptake of COS in R2, the CO2 enriched environment.
Technical Note: Sensitivity of 1-D smoke plume rise models to the inclusion of environmental wind drag
Authors: Freitas S. R. , Longo K. M. , Trentmann J. , Latham D.
Published: April 2010

Abstract. Vegetation fires emit hot gases and particles which are rapidly transported upward by the positive buoyancy generated by the combustion process. In general, the final vertical height that the smoke plumes reach is controlled by the thermodynamic stability of the atmospheric environment and the surface heat flux released by the fire. However, the presence of a strong horizontal wind can enhance the lateral entrainment and induce additional drag, particularly for small fires, impacting the smoke injection height. In this paper, we revisit the parameterization of the vertical transport of hot gases and particles emitted from vegetation fires, described in Freitas et al. (2007), to include the effects of environmental wind on transport and dilution of the smoke plume at its scale. This process is quantitatively represented by introducing an additional entrainment term to account for organized inflow of a mass of cooler and drier ambient air into the plume and its drag by momentum transfer. An extended set of equations including the horizontal motion of the plume and the additional increase of the plume radius is solved to simulate the time evolution of the plume rise and the smoke injection height. One-dimensional (1-D) model results are presented for two deforestation fires in the Amazon basin with sizes of 10 and 50 ha under calm and windy atmospheric environments. The results are compared to corresponding simulations generated by the complex non-hydrostatic three-dimensional (3-D) Active Tracer High resolution Atmospheric Model (ATHAM). We show that the 1-D model results compare well with the full 3-D simulations. The 1-D model may thus be used in field situations where extensive computing facilities are not available, especially under conditions for which several optional cases must be studied.
Secondary organic aerosol production from modern diesel engine emissions
Authors: Samy S. , Zielinska B.
Published: April 2010

Abstract. Secondary organic aerosol (SOA) production was observed at significant levels in a series of modern diesel exhaust (DE) aging experiments conducted at the European Outdoor Photoreactor/Simulation Chamber (EUPHORE). The greatest production occurred in DE with toluene addition experiments (>40%), followed by DE with HCHO (for OH radical generation) experiments. A small amount of SOA (3%) was observed for DE in dark with N2O5 (for NO3 radical production) experiments. The analysis for a limited number (54) of polar organic compounds (POC) was conducted to assess the composition of modern DE and the formation of photochemical transformation products. Distinct POC formation in light versus dark experiments suggests the role of OH initiated reactions in these chamber atmospheres. A trend of increasing concentrations of dicarboxylic acids in light versus dark experiments was observed when evaluated on a compound group basis. The four toluene addition experiments in this study were performed at different [tol]o/[NOx]o ratios and displayed an average SOA %yield (in relation to toluene) of 5.3±1.6%, which is compared to past chamber studies that evaluated the impact of [tol]o/[NOx]o on SOA production in more simplified mixtures.
Weather response to a large wind turbine array
Authors: Barrie D. B. , Kirk-Davidoff D. B.
Published: April 2010

Abstract. Electrical generation by wind turbines is increasing rapidly, and has been projected to satisfy 15% of world electric demand by 2030. The extensive installation of wind farms would alter surface roughness and significantly impact the atmospheric circulation due to the additional surface roughness forcing. This forcing could be changed deliberately by adjusting the attitude of the turbine blades with respect to the wind, which would enable the "management" of a large array of wind turbines. Using a General Circulation Model (GCM), we represent a continent-scale wind farm as a distributed array of surface roughness elements. Here we show that initial disturbances caused by a step change in roughness grow within four and a half days such that the flow is altered at synoptic scales. The growth rate of the induced perturbations is largest in regions of high atmospheric instability. For a roughness change imposed over North America, the induced perturbations involve substantial changes in the track and development of cyclones over the North Atlantic, and the magnitude of the perturbations rises above the level of forecast uncertainty.
Global model simulations of air pollution during the 2003 European heat wave
Authors: Ordóñez C. , Elguindi N. , Stein O. , Huijnen V. , Flemming J. , Inness A. , Flentje H. , Katragkou E. , Moinat P. , Peuch V.-H. , Segers A. , Thouret V. , Athier G. , van Weele M. , Zerefos C. S. , Cammas J.-P. , Schultz M. G.
Published: April 2010

Abstract. Three global Chemistry Transport Models – MOZART, MOCAGE, and TM5 – as well as MOZART coupled to the IFS meteorological model including assimilation of ozone (O3) and carbon monoxide (CO) satellite column retrievals, have been compared to surface measurements and MOZAIC vertical profiles in the troposphere over Western/Central Europe for summer 2003. The models reproduce the meteorological features and enhancement of pollution during the period 2–14 August, but not fully the ozone and CO mixing ratios measured during that episode. Modified normalised mean biases are around −25% (except ~5% for MOCAGE) in the case of ozone and from −80% to −30% for CO in the boundary layer above Frankfurt. The coupling and assimilation of CO columns from MOPITT overcomes some of the deficiencies in the treatment of transport, chemistry and emissions in MOZART, reducing the negative biases to around 20%. The high reactivity and small dry deposition velocities in MOCAGE seem to be responsible for the overestimation of O3 in this model. Results from sensitivity simulations indicate that an increase of the horizontal resolution to around 1°×1° and potential uncertainties in European anthropogenic emissions or in long-range transport of pollution cannot completely account for the underestimation of CO and O3 found for most models. A process-oriented TM5 sensitivity simulation where soil wetness was reduced results in a decrease in dry deposition fluxes and a subsequent ozone increase larger than the ozone changes due to the previous sensitivity runs. However this latest simulation still underestimates ozone during the heat wave and overestimates it outside that period. Most probably, a combination of the mentioned factors together with underrepresented biogenic emissions in the models, uncertainties in the modelling of vertical/horizontal transport processes in the proximity of the boundary layer as well as limitations of the chemistry schemes are responsible for the underestimation of ozone (overestimation in the case of MOCAGE) and CO found in the models during this extreme pollution event.
Global estimates of CO sources with high resolution by adjoint inversion of multiple satellite datasets (MOPITT, AIRS, SCIAMACHY, TES)
Authors: Kopacz M. , Jacob D. J. , Fisher J. A. , Logan J. A. , Zhang L. , Megretskaia I. A. , Yantosca R. M. , Singh K. , Henze D. K. , Burrows J. P. , Buchwitz M. , Khlystova I. , McMillan W. W. , Gille J. C. , Edwards D. P. , Eldering A. , Thouret V. , Nedelec P.
Published: April 2010

Abstract. We combine CO column measurements from the MOPITT, AIRS, SCIAMACHY, and TES satellite instruments in a full-year (May 2004–April 2005) global inversion of CO sources at 4°×5° spatial resolution and monthly temporal resolution. The inversion uses the GEOS-Chem chemical transport model (CTM) and its adjoint applied to MOPITT, AIRS, and SCIAMACHY. Observations from TES, surface sites (NOAA/GMD), and aircraft (MOZAIC) are used for evaluation of the a posteriori solution. Using GEOS-Chem as a common intercomparison platform shows global consistency between the different satellite datasets and with the in situ data. Differences can be largely explained by different averaging kernels and a priori information. The global CO emission from combustion as constrained in the inversion is 1350 Tg a−1. This is much higher than current bottom-up emission inventories. A large fraction of the correction results from a seasonal underestimate of CO sources at northern mid-latitudes in winter and suggests a larger-than-expected CO source from vehicle cold starts and residential heating. Implementing this seasonal variation of emissions solves the long-standing problem of models underestimating CO in the northern extratropics in winter-spring. A posteriori emissions also indicate a general underestimation of biomass burning in the GFED2 inventory. However, the tropical biomass burning constraints are not quantitatively consistent across the different datasets.
What caused extreme ozone concentrations over Cotonou in December 2005?
Authors: Minga A. , Thouret V. , Saunois M. , Delon C. , Serça D. , Mari C. , Sauvage B. , Mariscal A. , Leriche M. , Cros B.
Published: April 2010

Abstract. This paper reports the first record of extreme ozone measurements in Africa. As part of the AMMA program, the ozone vertical profile recorded on 20 December over Cotonou presents exceptionally high ozone concentrations with up to 295 ppb at 1 km altitude. Retroplumes from the Flexpart model show that the air masses sampled at 1 km over Cotonou on this day came from the burning area situated north-east of Cotonou and passed over Lagos, Nigeria, which is highly impacted by urban pollution. We used the Master Mechanism box model to simulate the chemical composition of the plume during its transit. We find that neither the biomass burning emissions of ozone precursors nor additional urban emissions from Lagos are high enough to simulate more than 120–150 ppb of ozone. The only way to reach almost 300 ppb of ozone within a few hours is to feed the air mass with large amounts of reactive VOCs as those recorded in the vicinity of petrochemical area. Sensitivity tests show that 250–600 ppb of VOCs combined with 35–80 ppb of NOx allow the ozone concentrations to be higher than 250 ppb. Nigeria is the first African country with gas extraction and petrochemical industries, and petrochemical explosions frequently happen in the vicinity of Lagos. The hypothesis of a petrochemical explosion in this area is the most likely scenario which could explain the 295 ppb ozone maximum measured over Cotonou, downwind of Lagos.
First remote sensing measurements of ClOOCl along with ClO and ClONO2 in activated and deactivated Arctic vortex conditions using new ClOOCl IR absorption cross sections
Authors: Wetzel G. , Oelhaf H. , Kirner O. , Ruhnke R. , Friedl-Vallon F. , Kleinert A. , Maucher G. , Fischer H. , Birk M. , Wagner G. , Engel A.
Published: April 2010

Abstract. Active chlorine species play a dominant role in the catalytic destruction of stratospheric ozone in the polar vortices during the late winter and early spring seasons. Recently, the correct understanding of the ClO dimer cycle was challenged by the release of new laboratory absorption cross sections (Pope et al., 2007) yielding significant model underestimates of observed ClO and ozone loss (von Hobe et al., 2007). Under this aspect, nocturnal Arctic stratospheric limb emission measurements carried out by the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) from Kiruna (Sweden) on 11 January 2001 and 20/21 March 2003 have been reanalyzed with regard to the chlorine reservoir species ClONO2 and the active species, ClO and ClOOCl (Cl2O2). New laboratory measurements of IR absorption cross sections of ClOOCl for various temperatures and pressures allowed for the first time the retrieval of ClOOCl mixing ratios from remote sensing measurements. High values of active chlorine (ClOx) of roughly 2.3 ppbv at 20 km were observed by MIPAS-B in the cold mid-winter Arctic vortex on 11 January 2001. While nighttime ClOOCl shows enhanced values of nearly 1.1 ppbv at 20 km, ClONO2 mixing ratios are less than 0.1 ppbv at this altitude. In contrast, high ClONO2 mixing ratios of nearly 2.4 ppbv at 20 km have been observed in the late winter Arctic vortex on 20 March 2003. No significant ClOx amounts are detectable on this date since most of the active chlorine has already recovered to its main reservoir species ClONO2. The observed values of ClOx and ClONO2 are in line with the established polar chlorine chemistry. The thermal equilibrium constants between the dimer formation and its dissociation, as derived from the balloon measurements, are on the lower side of reported data and in good agreement with values recommended by von Hobe et al. (2007). Calculations with the ECHAM/MESSy Atmospheric Chemistry model (EMAC) using established kinetics show similar chlorine activation and deactivation, compared to the measurements in January 2001 and March 2003, respectively.
Size-resolved aerosol water-soluble ionic compositions in the summer of Beijing: implication of regional secondary formation
Authors: Guo S. , Hu M. , Wang Z. B. , Slanina J. , Zhao Y. L.
Published: April 2010

Abstract. To characterize aerosol pollution in Beijing, size-resolved aerosols were collected by MOUDIs during CAREBEIJING-2006 field campaign at Peking University (urban site) and Yufa (upwind rural site). Fine particle concentrations (PM1.8 by MOUDI) were 99.8±77.4 μg/m3 and 78.2±58.4 μg/m3, with PM1.8/PM10 ratios of 0.64±0.08 and 0.76±0.08 at PKU and Yufa, respectively, and secondary compounds accounted for more than 50% in fine particles. PMF model analysis was used to resolve the particle modes. Three modes were resolved at Yufa, representing condensation, droplet and coarse mode. However, one more droplet mode with bigger size was resolved, which was considered probably from regional transport. Condensation mode accounted for 10%–60% of the total mass at both sites, indicating that the gas-to-particle condensation process was important in summer. The formation of sulfate was mainly attributed to in-cloud or aerosol droplet process (PKU 80%, Yufa 70%) and gas condensation process (PKU 14%, Yufa 22%). According to the thermodynamic instability of NH4NO3, size distributions of nitrate were classified as three categories by RH. The existence of Ca(NO3)2 in droplet mode indicated the reaction of HNO3 with crustal particles was also important in fine particles. A rough estimation was given that 69% of the PM10 and 87% of the PM1.8 in Beijing urban were regional contributions. Sulfate, ammonium and oxalate were formed regionally, with the regional contributions of 90%, 87% and 95% to PM1.8. Nitrate formation was local dominant. In summary regional secondary formation led to aerosol pollution in the summer of Beijing.
Ice nucleation properties of mineral dust particles: determination of onset RHi, IN active fraction, nucleation time-lag, and the effect of active sites on contact angles
Authors: Kulkarni G. , Dobbie S.
Published: April 2010

Abstract. A newly developed ice nucleation experimental set up was used to investigate the heterogeneous ice nucleation properties of three Saharan and one Spanish dust particle samples. It was observed that the spread in the onset relative humidities with respect to ice (RHi) for Saharan dust particles varied from 104% to 110%, whereas for the Spanish dust from 106% to 110%. The elemental composition analysis shows a prominent Ca feature in the Spanish dust sample which could potentially explain the differences in nucleation threshold. Although the spread in the onset RHi for the three Saharan dust samples were in agreement, the active fractions and nucleation time-lags calculated at various temperature and RHi conditions were found to differ. This could be due to the subtle variation in the elemental composition of the dust samples, and surface irregularities like steps, cracks, cavities etc. A combination of classical nucleation theory and active site theory is used to understand the importance of these surface irregularities on the nucleability parameter, contact angle that is widely used in ice cloud modeling. These calculations show that the surface irregularities can reduce the contact angle by approximately 10 degrees.
Source attribution and interannual variability of Arctic pollution in spring constrained by aircraft (ARCTAS, ARCPAC) and satellite (AIRS) observations of carbon monoxide
Authors: Fisher J. A. , Jacob D. J. , Purdy M. T. , Kopacz M. , Le Sager P. , Carouge C. , Holmes C. D. , Yantosca R. M. , Batchelor R. L. , Strong K. , Diskin G. S. , Fuelberg H. E. , Holloway J. S. , Hyer E. J. , McMillan W. W. , Warner J. , Streets D. G. , Zhang Q. , Wang Y. , Wu S.
Published: April 2010

Abstract. We use aircraft observations of carbon monoxide (CO) from the NASA ARCTAS and NOAA ARCPAC campaigns in April 2008 together with multiyear (2003–2008) CO satellite data from the AIRS instrument and a global chemical transport model (GEOS-Chem) to better understand the sources, transport, and interannual variability of pollution in the Arctic in spring. Model simulation of the aircraft data gives best estimates of CO emissions in April 2008 of 26 Tg month−1 for Asian anthropogenic, 9.4 for European anthropogenic, 4.1 for North American anthropogenic, 15 for Russian biomass burning (anomalously large that year), and 23 for Southeast Asian biomass burning. We find that Asian anthropogenic emissions are the dominant source of Arctic CO pollution everywhere except in surface air where European anthropogenic emissions are of similar importance. Russian biomass burning makes little contribution to mean CO (reflecting the long CO lifetime) but makes a large contribution to CO variability in the form of combustion plumes. Analysis of two pollution events sampled by the aircraft demonstrates that AIRS can successfully observe pollution transport to the Arctic in the mid-troposphere. The 2003–2008 record of CO from AIRS shows that interannual variability averaged over the Arctic cap is very small. AIRS CO columns over Alaska are highly correlated with the Ocean Niño Index, suggesting a link between El Niño and Asian pollution transport to the Arctic. AIRS shows lower-than-average CO columns over Alaska during April 2008, despite the Russian fires, due to a weakened Aleutian Low hindering transport from Asia and associated with the moderate 2007–2008 La Niña. This suggests that Asian pollution influence over the Arctic may be particularly large under strong El Niño conditions.
Nucleation events in the continental boundary layer: Influence of physical and meteorological parameters
Authors: Boy M. , Kulmala M.
Published: April 2010

Abstract. The relationship between nucleation events and numerous physical and meteorological parameters was analysed using data collected at the Station for Measuring Forest Ecosystem-Atmosphere Relations (SMEAR II) in Hyytiälä, Finland. To do this, measurements of solar radiation (ultraviolet [UV], global, photosynthetically active radiation [PAR], net, reflected global radiation and reflected PAR), gas concentrations, temperature, humidity, wind direction, horizontal and vertical wind speed, horizontal and vertical wind variances and particle concentrations were collected over a 4 year period. For the year 1999 a detailed analysis of data were completed by examining parameters in order to determine the physical and meteorological conditions favourable to the formation of new particles. A comparison of different wavelength bands during the bursts of new particles led to the suggestion, that UV-A solar radiation seems to be the most probable radiation band concerning the photochemical reactions involved in the production of condensable vapours. Furthermore a high correlation between the daily curves of UV-A irradiance and the concentration of 3 - 5 nm particles was found throughout the year and examples will be given for two days. During the whole year the concentration of H2O is very low at times nucleation occurs compared to the average of the corresponding month. Especially in June and July many non-event days with high solar irradiance show high amounts of water molecules. To combine these results a "nucleation parameter" was calculated for the year 1999, by dividing UV-A solar radiation by the concentration of H2O and temperature. Throughout the year nearly all nucleation event days reach a value of the "nucleation parameter" of at least 5.4 x 10-25 W m molecules-1 K-1.  Non-event days with high values (> 2.7 x 10-25 W m molecules-1 K-1) are mostly accompanied by high concentrations of existing particles.
Chemistry-transport modeling of the satellite observed distribution of tropical troposheric ozone
Authors: Peters W. , Krol M. , Dentener F. , Thompson A. M. , Lelieveld J.
Published: April 2010

Abstract. We have compared the 14-year record of satellite derived tropical tropospheric ozone columns (TTOC) from the NIMBUS--7 Total Ozone Mapping Spectrometer (TOMS) to TTOC calculated by achemistry-transport model (CTM). An objective measure of error, based on the zonal distribution of TTOC in the tropics, is applied to perform this comparison systematically. In addition, the sensitivity of the model to several key processes in the tropics is quantified to select directions for future improvements. The comparisons indicate a widespread, systematic (20%) discrepancy over the tropical Atlantic Ocean, which maximizes during austral Spring. Although independent evidence from ozonesondes shows that some of the disagreement is due to satellite overestimate of TTOC, the Atlantic mismatch is largely due to a misrepresentation of seasonally recurring processes in the model. Only minor differences between the model and observations over the Pacific occur, mostly due to interannual variability not captured by the model. Although chemical processes determine the TTOC extent, dynamical processes dominate the TTOC distribution, as the use of actual meteorology pertaining to the year of observations always leads to a better agreement with TTOC observations than using a random year or a climatology. The modeled TTOC is remarkably insensitive to many model parameters due to efficient feedbacks in the ozone budget. Nevertheless, the simulations would profit from an improved biomass burning calendar, as well as from an increase in NOx abundances in free tropospheric biomass burning plumes. The model showed the largest response to lightning NOx emissions, but systematic improvements could not be found. The use of multi-year satellite derived tropospheric data to systematically test and improve a CTM is a promising new addition to existing methods of model validation, and is a first step to integrating tropospheric satellite observations into global ozone modeling studies. Conversely, the CTM may suggest improvements to evolving satellite retrievals for tropospheric ozone.
Using 14C, 13C, 18O and 17O isotopic variations to provide insights into the high northern latitude surface CO inventory
Authors: Röckmann T. , Jöckel P. , Gros V. , Bräunlich M. , Possnert G. , Brenninkmeijer C. A. M.
Published: April 2010

Abstract. Measurements of the complete isotopic composition of atmospheric CO (3CO, 14CO, C17O, C18O) have been carried out at the high northern latitude stations Spitsbergen, Norway, and Alert, Canada. The annual changes of the isotope signatures reflect the seasonally varying contributions from the individual CO sources and the OH sink. Short-term variability is small at the remote sampling locations. Nevertheless, the interannual variability is considerable, in particular for the summer minimum. The most prominent event was a strong increase in CO in 1998 that persisted for several months. Using the isotope signatures it is possible to clearly identify extraordinarily strong biomass burning during that season as the cause for this large-scale CO anomaly. In 1997, on the other hand, biomass burning emissions were very low, leading to an unusually low summer minimum and corresponding isotope signatures. The results underscore that monitoring of CO and its isotopic composition at remote high latitude stations is a valuable tool to better understand long-term variations of CO that are representative for the whole high northern latitude region.
Modelling the contribution of sea salt and dimethyl sulfide derived aerosol to marine CCN
Authors: Yoon Y. J. , Brimblecombe P.
Published: April 2010

Abstract. The concentration of cloud condensation nuclei (CCN) in the marine boundary layer (MBL) was estimated from dimethyl sulfide (DMS) flux, sea salt (SS) emission, and aerosols entrained from the free troposphere (FT). Only under clean air conditions, did the nucleation of DMS derived sulfur (DMS CCN) contribute significantly to the MBL CCN. The accommodation coefficient for sulfuric acid mass transfer was found to be a very important parameter in the modeling the contribution of DMS to MBL CCN. The relationship between seawater DMS and MBL CCN was found to be non-linear mainly due to the transfer processes of sulfuric acid onto aerosols. In addition, sea salt derived CCN (SS CCN) and entrained aerosol from the FT (FT CCN) affected the MBL CCN directly, by supplying CCN, and indirectly, by behaving as an efficient sink for sulfuric acid. The SS CCN explained more than 50% of the total predicted MBL CCN when wind speeds were moderate and high. Sea salt and FT aerosol may often be more efficient sources of MBL CCN than DMS.
Surface ozone depletion episodes in the Arctic and Antarctic from historical ozonesonde records
Authors: Tarasick D. W. , Bottenheim J. W.
Published: April 2010

Abstract. Episodes of ozone depletion in the lowermost Arctic atmosphere (0--2 km) at polar sunrise have been intensively studied at Alert, Canada, and are thought to result from catalytic reactions involving bromine. Recent observations of high concentrations of tropospheric BrO over large areas of the Arctic and Antarctic suggest that such depletion events should also be seen by ozonesondes at other polar stations. An examination of historical ozonesonde records shows that such events occur frequently at Alert, Eureka and Resolute, but much less frequently at Churchill and at other stations. The differences appear to be related to differences in average springtime surface temperatures. The long record at Resolute shows depletions since 1966, but with an increase in their frequency over the period 1966--2000 of 0.66 ± 0.59% per year (95% confidence limits), explaining the apparent increase of Hg in Arctic biota in recent times.
Homogeneous nucleation of NAD and NAT in liquid stratospheric aerosols: insufficient to explain denitrification
Authors: Knopf D. A. , Koop T. , Luo B. P. , Weers U. G. , Peter T.
Published: April 2010

Abstract. The nucleation of NAD and NAT from HNO3/H2O and HNO3/H2SO4/H2O solution droplets is investigated both theoretically and experimentally with respect to the formation of polar stratospheric clouds (PSCs). Our analysis shows that homogeneous NAD and NAT nucleation from liquid aerosols is insufficient to explain the number densities of large nitric acid containing particles recently observed in the Arctic stratosphere. This conclusion is based on new droplet freezing experiments employing optical microscopy combined with Raman spectroscopy. The homogeneous nucleation rate coefficients of NAD and NAT in liquid aerosols under polar stratospheric conditions derived from the experiments are < 2 x 10-5 cm-3 s-1 and < 8 x 10-2 cm-3 s-1, respectively. These nucleation rate coefficients are smaller by orders of magnitude than the value of ~103 cm-3 s-1 used in a recent denitrification modelling study that is based on a linear extrapolation of laboratory nucleation data to stratospheric conditions (Tabazadeh et al., Science, 291, 2591--2594, 2001). We show that this linear extrapolation is in disagreement with thermodynamics and with experimental data and, therefore, must not be used in microphysical models of PSCs. Our analysis of the experimental data yields maximum hourly production rates of nitric acid hydrate particles per cm3 of air of about 3 x 10-10 cm-3 (air) h-1 under polar stratospheric conditions. Assuming PSC particle production to proceed at this rate for two months we arrive at particle number densities of < 5 x 10-7 cm-3, much smaller than the value of ~10-4 cm-3 reported in recent field observations. In addition, the nitric acid hydrate production rate inferred from our data is much smaller than that required to reproduce the observed denitrification in the modelling study mentioned above. This clearly shows that homogeneous nucleation of NAD and NAT from liquid supercooled ternary solution aerosols cannot explain the observed polar denitrification.
Virtual disjunct eddy covariance measurements of organic compound fluxes from a subalpine forest using proton transfer reaction mass spectrometry
Authors: Karl T. G. , Spirig C. , Rinne J. , Stroud C. , Prevost P. , Greenberg J. , Fall R. , Guenther A.
Published: April 2010

Abstract. A `virtual' disjunct eddy covariance (vDEC) device was tested with field measurements of biogenic VOC fluxes at a subalpine forest site in the Rocky Mountains of the USA. A PTR-MS instrument was used as the VOC sensor. Daily peak emission fluxes of 2-methyl-3-buten-2-ol (MBO), methanol, acetone and acetaldehyde were around 1.5, 1, 0.8 and 0.4 mg m-2 h-1, respectively. High pass filtering due to long sampling lines was investigated in laboratory experiments, and suggested that VOC losses in PTFA lines are generally governed by diffusion laws. Memory effects and surface reactions did not seem to play a dominant role. Model estimates of MBO fluxes compared well with measured fluxes. The results also suggest that latent heat and sensible heat fluxes are reasonably well correlated with VOC fluxes and could be used to predict variations in VOC emissions. The release of MBO, methanol, acetone and acetaldehyde resulted in significant change of tropospheric oxidant levels and a 10--40% increase in ozone levels, as inferred from a photochemical box model. We conclude that vDEC with a PTR-MS instrument is a versatile tool for simultaneous field analysis of multiple VOC fluxes.
Tropical cirrus and water vapor: an effective Earth infrared iris feedback?
Authors: Fu Q. , Baker M. , Hartmann D. L.
Published: April 2010

Abstract. We revisit a model of feedback processes proposed by Lindzen et al. (2001), in which an assumed 22% reduction in the area of tropical high clouds per degree increase in sea surface temperature produces negative feedbacks associated with upper tropospheric water vapor and cloud radiative effects. We argue that the water vapor feedback is overestimated in Lindzen et al. (2001) by at least 60%, and that the high cloud feedback is small. Although not mentioned by Lindzen et al. (2001), tropical low clouds make a significant contribution to their negative feedback, which is also overestimated. Using more realistic parameters in the model of Lindzen et al. (2001), we obtain a feedback factor in the range of -0.15 to -0.51, compared to their larger negative feedback factor of -0.45 to -1.03. It is noted that our feedback factor could still be overestimated due to the assumption of constant low cloud cover in the simple radiative-convective model.
On the origin of tropospheric O3 over the Indian Ocean during the winter monsoon: African biomass burning vs. stratosphere-troposphere exchange
Authors: de Laat A. T. J.
Published: April 2010

Abstract. This study investigates the origin of a commonly observed feature in the O3 profiles: mid tropospheric O3 maxima (300--500 hPa) over the tropical Indian Ocean. A comparison and analysis of model simulations, using a 3-D global climate-chemistry model, and measured O3 profiles from the INDOEX campaign is presented. European Centre for Medium-Range Weather Forecast (ECMWF) meteorological analyses have been assimilated into the 3-D model to represent actual meteorology. The model realistically simulates the observed mid-tropospheric O3 maxima. The analysis of the model simulations shows that the major source of the mid-tropospheric O3 maxima is advection of polluted air masses from continental biomass burning areas over Africa, with generally only a small contribution of stratospheric O3. Previous studies hinted at stratosphere-troposphere exchange (STE) along the subtropical jet (STJ) as the primary source of the mid-tropospheric O3 maxima over the Indian Ocean. Analysis of the model simulations shows that the mechanism causing the mid-tropospheric transport of African biomass burning pollution and stratospheric air masses are frontal zones or waves passing along the subtropical jets, causing advection of tropical air masses in the prefrontal (equatorward) zone. Furthermore, the frontal zones or waves also cause STE at the poleward side of the STJ. The model simulations also indicate that the contribution of STE in general is minor compared to advection and in situ tropospheric production of O3 for the mid-tropospheric O3 budget over the Indian Ocean region.
An exploration of ozone changes and their radiative forcing prior to the chlorofluorocarbon era
Authors: Shindell D. T. , Faluvegi G.
Published: April 2010

Abstract. Using historical observations and model simulations, we investigate ozone trends prior to the mid-1970s onset of halogen-induced ozone depletion. Though measurements are quite limited, an analysis based on multiple, independent data sets (direct and indirect) provides better constraints than any individual set of observations. We find that three data sets support an apparent long-term stratospheric ozone trend of -7.2 ± 2.3 DU during 1957-1975, which modeling attributes primarily to water vapor increases. The results suggest that 20th century stratospheric ozone depletion may have been roughly 50% more than is generally supposed. Similarly, three data sets support tropospheric ozone increases over polluted Northern Hemisphere continental regions of 8.2 ± 2.1 DU during this period, which are mutually consistent with the stratospheric trends. As with paleoclimate data, which is also based on indirect proxies and/or limited spatial coverage, these results must be interpreted with caution. However, they provide the most thorough estimates presently available of ozone changes prior to the coincident onset of satellite data and halogen dominated ozone changes. If these apparent trends were real, the radiative forcing by stratospheric ozone since the 1950s would then have been -0.15 ± 0.05 W/m2, and -0.2 W/m2 since the preindustrial. For tropospheric ozone, it would have been 0.38 ± 0.10 W/m2 since the late 1950s. Combined with even a very conservative estimate of tropospheric ozone forcing prior to that time, this would be larger than current estimates since 1850 which are derived from models that are even less well constrained. These calculations demonstrate the importance of gaining a better understanding of historical ozone changes.
The influence of cloud chemistry on HOx and NOx in the moderately polluted marine boundary layer: a 1-D modelling study
Authors: Williams J. E. , Dentener F. J. , van den Berg A. R.
Published: April 2010

Abstract. A 1-D marine stratocumulus cloud model has been supplemented with a comprehensive and up-to-date aqueous phase chemical mechanism for the purpose of assessing the impact that the presence of clouds has on gas phaseHOx, NOx and O3 budgets in the marine boundary layer. The simulations presented here indicate that cloud may act as a heterogeneous source of HONOg. The conversion of HNO4(g) at moderate pH (~ 4.5) is responsible for this, and, to a lesser extent, the photolysis of nitrate (NO3-). The effect of introducing deliquescent aerosol on the simulated increase of HONOg is negligible. The most important consequences of this elevation in HONOg are that, in the presence of cloud, gas phase concentrations of NOx species increase by a factor of 2, which minimises the simulated decrease in O3(g), and results in a regeneration of OHg. This partly compensates for the removal of OHg by direct phase transfer into the cloud and may have important implications regarding the oxidising capacity of the marine boundary layer.
Tropospheric NO2 columns: a comparison between model and retrieved data from GOME measurements
Authors: Lauer A. , Dameris M. , Richter A. , Burrows J. P.
Published: April 2010

Abstract. Tropospheric NO2 plays a variety of significant roles in atmospheric chemistry. In the troposphere it is one of the most significant precursors of photochemical ozone (O3) production and nitric acid (HNO3). In this study tropospheric NO2 columns were calculated by the fully coupled chemistry-climate model ECHAM4.L39(DLR)/CHEM. These have been compared with tropospheric NO2 columns, retrieved using the tropospheric excess method from measurements by the Global Ozone Monitoring Experiment (GOME) of up-welling earthshine radiance and the extraterrestrial irradiance. GOME is part of the core payload of the second European Research Satellite (ERS-2). For this study the first five years of GOME measurements have been used. The period of five years of observational data is sufficiently long to facilitate for the first time a comparison based on climatological averages with global coverage, focussing on the geographical distribution of the tropospheric NO2. A new approach of analysing regional differences (i.e. on continental scales) by calculating individual averages for different environments provides more detailed information about specific NOx sources and of their seasonal variations. The results obtained enable the validity of the model NO2 source distribution and the assumptions used to separate tropospheric and stratospheric parts of the NO2 column amount from the satellite measurements to be investigated.
NAT-rock formation by mother clouds: a microphysical model study
Authors: Fueglistaler S. , Luo B.P. , Voigt C. , Carslaw K.S. , Peter Th.
Published: April 2010

Abstract. Polar stratospheric clouds (PSCs) of type 1a or 1a-enh containing high number densities of nitric acid trihydrate (NAT) particles, can act as mother clouds for extremely large NAT particles, termed NAT-rocks, provided the air below the clouds is supersaturated with respect to NAT. Individual NAT particles at the cloud base fall into undepleted gas phase and rapidly accelerate due to a positive feedback between their growth and sedimentation. The resulting reduction in number density is further enhanced by the strong HNO3 depletion within a thin layer below the mother cloud, which delays subsequent particles. This paper introduces the basic microphysical principles behind this mother cloud/NAT-rock mechanism, which produces 10-4 cm-3 NAT-rocks with radii around 10 mm some kilometers below the mother cloud. The mechanism does not require selective nucleation and works even for a monodisperse particle size distribution in the mother cloud.
In-situ observations of aerosol particles remaining from evaporated cirrus crystals: Comparing clean and polluted air masses
Authors: Seifert M. , Ström J. , Krejci R. , Minikin A. , Petzold A. , Gayet J.-F. , Schumann U. , Ovarlez J.
Published: April 2010

Abstract. In-situ observations of aerosol particles contained in cirrus crystals are presented and compared to interstitial aerosol size distributions (non-activated particles in between the cirrus crystals). The observations were conducted in cirrus clouds in the Southern and Northern Hemisphere mid-latitudes during the INCA project. The first campaign in March and April 2000 was performed from Punta Arenas, Chile (54°S) in pristine air. The second campaign in September and October 2000 was performed from Prestwick, Scotland (53°N) in the vicinity of the North Atlantic flight corridor. Size distribution measurements of crystal residuals (particles remaining after evaporation of the crystals) show that small aerosol particles (Dp< 0.1 mm) dominate the number density of residuals. The crystal residual size distributions were significantly different in the two campaigns. On average the residual size distributions were shifted towards larger sizes in the Southern Hemisphere. For a given integral residual number density, the calculated particle volume was on average three times larger in the Southern Hemisphere. This may be of significance to the vertical redistribution of aerosol mass by clouds in the tropopause region. In both campaigns the mean residual size increased slightly with increasing crystal number density. The form of the residual size distribution did not depend on temperature as one might have expected considering different modes of nucleation. The observations of ambient aerosol particles were consistent with the expected higher pollution level in the Northern Hemisphere. The fraction of residual particles only contributes to approximately a percent or less of the total number of particles, which is the sum of the residual and interstitial particles. Excellent agreement between the CVI and FSSP-300 probes was found supporting the assumption that each crystal is associated with only one residual particle.
A discussion on the determination of atmospheric OH and its trends
Authors: Jöckel P. , Brenninkmeijer C. A. M. , Crutzen P. J.
Published: April 2010

Abstract. The oxidation efficiency of the troposphere is largely determined by the hydroxyl radical and its global distribution. Its presence limits the lifetime of most trace gases. Because of the great importance of several of these gases for climate, ozone budget and OH itself, it is of fundamental importance to acquire knowledge about atmospheric OH and possible trends in its concentrations. In the past, average concentrations of OH and trends were largely derived using industrially produced CH3CCl3 as a chemical tracer. The analyses have given valuable, but also rather uncertain results. In this paper we describe an idealized computer aided tracer experiment which has as one of its goals to derive tracer concentration weighted, global average , where the temporal and spatial OH distribution is prescribed and k is the reaction rate coefficient of OH with a hitherto never produced (Gedanken) tracer, which is injected at a number of surface sites in the atmosphere in well known amounts over a given time period. Using a three-dimensional (3-D) time-dependent chemistry transport model,  can be accurately determined from the calculated 3-D tracer distribution. It is next explored how well  can be retrieved solely from tracer measurements at a limited number of surface sites. The results from this analysis are encouraging enough to actually think about the feasibility to carry out a global dedicated tracer experiment to derive  and its temporal trends. However, before that, we propose to test the methods that are used to derive , so far largely using CH3CCl3, with an idealized tracer experiment, in which a global chemistry transport model is used to calculate the ``Gedanken'' tracer distribution, representing the real 3-D world, from which  is derived, using only the tracer information from a limited set of surface sites. We propose here that research groups which are, or will be, involved in global average OH studies to participate in such an inter-comparison of methods, organized and over-seen by a committee appointed by the International Global Atmospheric Chemistry (IGAC) program.