bluuebunny/crossref_metadata_2025 huggingface dataset:
Homogeneous nucleation of sulfuric acid and water mixture: experimental setup and first results
Authors: Brus D. , Hyvärinen A.-P. , Viisanen Y. , Kulmala M. , Lihavainen H.
Published: April 2010

Abstract. In this study we introduce a new flow tube suitable for binary and ternary homogeneous nucleation studies. The production of sulfuric acid and water vapor mixture, the experimental setup and the method of sulfuric acid concentration determination are discussed in detail. Wall losses were estimated from the measured sulfuric acid concentration profiles along the flow tube and compared to a theoretical prediction. In this investigation the experimental evidence of new particle formation was observed at a concentration of 109 molecules cm−3 of sulfuric acid and the nucleation rates measured at three relative humidities (RH) 10, 30 and 50%, cover six orders of magnitude, from 10−3 to 103 particles cm−3. Particle free air was used as a carrier gas. Our initial results are compared to the theoretical prediction of binary homogeneous nucleation, to results obtained by other investigators, and to atmospheric nucleation.
Atmospheric nitrogen budget in Sahelian dry savannas
Authors: Delon C. , Galy-Lacaux C. , Boone A. , Liousse C. , Serça D. , Adon M. , Diop B. , Akpo A. , Lavenu F. , Mougin E. , Timouk F.
Published: April 2010

Abstract. The atmospheric nitrogen budget depends on emission and deposition fluxes both as reduced and oxidized nitrogen compounds. In this study, a first attempt at estimating the Sahel nitrogen budget for the year 2006 is made, through measurements and simulations at three stations from the IDAF network situated in dry savanna ecosystems. Dry deposition fluxes are estimated from measurements of NO2, HNO3 and NH3 gaseous concentrations and from simulated dry deposition velocities, and wet deposition fluxes are calculated from NH4+ and NO3− concentrations in samples of rain. Emission fluxes are estimated including biogenic emission of NO from soils (an Artificial Neural Network module has been inserted into the ISBA-SURFEX surface model), emission of NOx and NH3 from domestic fires and biomass burning, and volatilization of NH3 from animal excreta. Uncertainties are calculated for each contribution of the budget. This study uses original and unique data from remote and hardly-ever-explored regions.The monthly evolution of oxidized N compounds shows that emission and deposition increase at the beginning of the rainy season because of large emissions of biogenic NO (pulse events). Emission of oxidized compounds is dominated by biogenic emission from soils (domestic fires and biomass burning of oxidized compounds account for 0 to 13% at the most at the annual scale, depending on the station), whereas emission of NH3 is dominated by the process of volatilization from soils. At the annual scale, the average gaseous dry deposition accounts for 47% of the total estimated deposition flux, for both oxidized and reduced compounds. The average estimated wet plus dry deposition flux in dry savanna ecosystems is 7.5±1.8 kgN ha−1 yr−1, with approximately 30% attributed to oxidized compounds, and the rest attributed to NHx. The average estimated emission flux ranges from 8.4(±3.8) to 12.4(±5.9) kgN ha−1 yr−1, dominated by NH3 volatilization (72–82%) and biogenic emission from soils (11–17%), depending on the applied volatilization rate of NH3. While larger, emission fluxes are on the same order of magnitude as deposition fluxes. The main uncertainties are linked to the NH3 emission from volatilization. When scaled up from the 3 measurement sites to the Sahelian region (12° N:18° N, 15° W:10° E), the estimated total emission ranges from 2(±0.9) to 3(±1.4) TgN yr−1, depending on the applied volatilization rate of NH3 and estimated total deposition is 1.8(±0.4) TgN yr−1. The dry savanna ecosystems of the Sahel contribute around 2% to the global (biogenic + anthropogenic) nitrogen budget.
Effects of resolution on the relative importance of numerical and physical horizontal diffusion in atmospheric composition modelling
Authors: D'Isidoro M. , Maurizi A. , Tampieri F.
Published: April 2010

Abstract. Numerical diffusion induced by advection has a large influence on concentration of substances in atmospheric composition models. At coarse resolution numerical effects dominate, whereas at increasing model resolution a description of physical diffusion is needed. A method to investigate the effects of changing resolution and Courant number is defined here and is applied to the WAF advection scheme (used in BOLCHEM), evidencing a sub-diffusive process. The spread rate from an instantaneous source caused by numerical diffusion is compared to that produced by the physical diffusion necessary to simulate unresolved turbulent motions. The time at which the physical diffusion process overpowers the numerical spread is estimated, and it is shown to reduce as the resolution increases, and to increase with wind velocity.
Distribution of gaseous and particulate organic composition during dark α-pinene ozonolysis
Authors: Camredon M. , Hamilton J. F. , Alam M. S. , Wyche K. P. , Carr T. , White I. R. , Monks P. S. , Rickard A. R. , Bloss W. J.
Published: April 2010

Abstract. Secondary Organic Aerosol (SOA) affects atmospheric composition, air quality and radiative transfer, however major difficulties are encountered in the development of reliable models for SOA formation. Constraints on processes involved in SOA formation can be obtained by interpreting the speciation and evolution of organics in the gaseous and condensed phase simultaneously. In this study we investigate SOA formation from dark α-pinene ozonolysis with particular emphasis upon the mass distribution of gaseous and particulate organic species. A detailed model for SOA formation is compared with the results from experiments performed in the EUropean PHOtoREactor (EUPHORE) simulation chamber, including on-line gas-phase composition obtained from Chemical-Ionization-Reaction Time-Of-Flight Mass-Spectrometry measurements, and off-line analysis of SOA samples performed by Ion Trap Mass Spectrometry and Liquid Chromatography. The temporal profile of SOA mass concentration is relatively well reproduced by the model. Sensitivity analysis highlights the importance of the choice of vapour pressure estimation method, and the potential influence of condensed phase chemistry. Comparisons of the simulated gaseous- and condensed-phase mass distributions with those observed show a generally good agreement. The simulated speciation has been used to (i) propose a chemical structure for the principal gaseous semi-volatile organic compounds and condensed monomer organic species, (ii) provide evidence for the occurrence of recently suggested radical isomerisation channels not included in the basic model, and (iii) explore the possible contribution of a range of accretion reactions occurring in the condensed phase. We find that oligomer formation through esterification reactions gives the best agreement between the observed and simulated mass spectra.
A new modeling tool for the diffusion of gases in ice or amorphous binary mixture in the polar stratosphere and the upper troposphere
Authors: Varotsos C. A. , Zellner R.
Published: April 2010

Abstract. To elaborate stratospheric ozone depletion processes, measurements of diffusion coefficients of selected gas phase molecules (i.e. HCl, CH3OH, HCOOH and CH3COOH; Katsambas et al., 1997; Kondratyev and Varotsos, 1996; Varotsos et al., 1994, 1995) in ice in the temperature range 170–195 K have been analyzed with respect to the mechanisms and rates of diffusion. It is argued that the diffusion in ice of these compounds is governed by a vacancy – mediated mechanism, i.e. H2O vacancies are required to diffuse to lattice sites adjacent to these compounds prior to the diffusion of the corresponding molecule into the vacancy sites. In addition, we show that the diffusion coefficients of these compounds exhibit a specific interconnection, i.e. a linear relationship holds between the logarithm of the pre-exponential factor, Do, and the activation energy E. The physical meaning of this interconnection is discussed.
Single ice crystal measurements during nucleation experiments with the depolarization detector IODE
Authors: Nicolet M. , Stetzer O. , Lüönd F. , Möhler O. , Lohmann U.
Published: April 2010

Abstract. In order to determine the efficiency of different aerosol particles to nucleate ice, an Ice Optical DEpolarization detector (IODE) was developed to distinguish between water droplets and ice crystals in ice nucleation chambers. A laser beam polarized linearly (power: 50 mW, wavelength: 407 nm) is directed through the chamber. The scattered light intensity from particles is measured at a scattering angle of Θ=175° in both polarization components (parallel and perpendicular). The ratio between the perpendicular intensity over the total one yields the depolarization ratio δ. Single particle detection is possible, using a peak detection algorithm. For high particle concentrations, a real-time signal averaging method can also be run simultaneously. The IODE detector was used in connection with the Zurich ice nucleation chamber during the ICIS 2007 workshop where ice nucleation experiments were performed with several aerosol types. In presence of ice crystals, a depolarization ratio could be measured on a particle-by-particle basis. Mean values of δ ranged from 0.24 to 0.37 and agree well with theoretical calculations.
Solar cycle signals in sea level pressure and sea surface temperature
Authors: Roy I. , Haigh J. D.
Published: April 2010

Abstract. We identify solar cycle signals in 155 years of global sea level pressure (SLP) and sea surface temperature (SST) data using a multiple linear regression approach. In SLP we find in the North Pacific a statistically significant weakening of the Aleutian Low and a northward shift of the Hawaiian High in response to higher solar activity, confirming the results of previous authors using different techniques. We also find a weak but broad reduction in pressure across the equatorial Pacific. In SST we identify a weak El Niño-like pattern in the tropics for the 155 year period, unlike the strong La Niña-like signal found recently by some other authors. We show that the latter have been influenced by the technique of compositing data from peak years of the sunspot cycle because these years have often coincided with the negative phase of the ENSO cycle. Furthermore, the date of peak annual sunspot number (SSN) generally falls a year or more in advance of the broader maximum of the 11-year solar cycle so that analyses which incorporate data from all years represent more coherently the difference between periods of high and low solar activity on these timescales. We also find that studies of the solar signal in SST over the second half of the 20th century may alias as ENSO signal if this is not properly taken into account.
Effect of hygroscopic seeding on warm rain clouds – numerical study using a hybrid cloud microphysical model
Authors: Kuba N. , Murakami M.
Published: April 2010

Abstract. The effect of hygroscopic seeding on warm rain clouds was examined using a hybrid cloud microphysical model combining a Lagrangian Cloud Condensation Nuclei (CCN) activation model, a semi-Lagrangian droplet growth model, and an Eulerian spatial model for advection and sedimentation of droplets. This hybrid cloud microphysical model accurately estimated the effects of CCN on cloud microstructure and suggested the following conclusions for a moderate continental air mass (an air mass with a large number of background CCN). (1) Seeding can hasten the onset of surface rainfall and increase the accumulated amount of surface rainfall if the amount and radius of seeding particles are appropriate. (2) The optimal radius of monodisperse particles to increase rainfall becomes larger with the increase in the total mass of seeding particles. (3) Seeding with salt micro-powder can hasten the onset of surface rainfall and increase the accumulated amount of surface rainfall if the amount of seeding particles is sufficient. (4) Seeding by a hygroscopic flare decreases rainfall in the case of large updraft velocity (shallow convective cloud) and increases rainfall slightly in the case of small updraft velocity (stratiform cloud). (5) Seeding with hygroscopic flares including ultra-giant particles (r>5 μm) hastens the onset of surface rainfall but may not significantly increase the accumulated surface rainfall amount. (6) Hygroscopic seeding increases surface rainfall by two kinds of effects: the "competition effect" by which large soluble particles prevent the activation of smaller particles and the "raindrop embryo effect" in which giant soluble particles can immediately become raindrop embryos. In some cases, one of the effects works, and in other cases, both effects work, depending on the updraft velocity and the amount and size of seeding particles.
Emissions of air-borne mercury from five municipal solid waste landfills in Guiyang and Wuhan, China
Authors: Li Z.-G. , Feng X. , Li P. , Liang L. , Tang S.-L. , Wang S.-F. , Fu X.-W. , Qiu G.-L. , Shang L.-H.
Published: April 2010

Abstract. China disposes of bulk Municipal Solid Waste (MSW) by landfilling, resulting in a large quantity of mercury that enters landfills through waste. A detailed study on atmospheric mercury emissions from MSW landfills in China is necessary to understand mercury behavior from this source. Between 2003 and 2006, mercury airborne emissions through different pathways, as well as mercury speciation in Landfill Gas (LFG) were measured at 5 MSW landfills in Guiyang and Wuhan, China. The results showed that mercury content in the substrate increased the magnitude of mercury emissions, with the highest emission rate measured at the working face and in uncovered waste areas, and the lowest measured near soil covers and vegetated areas. Meteorological parameters, especially solar radiation, influenced the diurnal pattern of mercury surface-air emissions. Total Gaseous Mercury (TGM) in LFG varied from 2.0 to 1406.0 ng m−3, Monomethyl Mercury (MMHg) and Dimethyl Mercury (DMHg) in LFG averaged at 1.93 and 9.21 ng m−3, and accounted for 0.51% and 1.79% of the TGM in the LFG, respectively. Total mercury emitted from the five landfills ranged from 17 to 3300 g yr−1, with the highest from the working face, then soil covering, and finally the vent pipes.
Sensitivity of tracer transport to model resolution, prescribed meteorology and tracer lifetime in the general circulation model ECHAM5
Authors: Aghedo A. M. , Rast S. , Schultz M. G.
Published: April 2010

Abstract. Atmospheric transport of traces gases and aerosols plays an important role in the distribution of air pollutants and radiatively active compounds. For model simulations of chemistry-climate interactions it is important to know how the transport of tracers depends on the geographical resolution of the general circulation model. However, this aspect has been scarcely investigated until now. Here, we analyse tracer transport in the ECHAM5 general circulation model using 6 independent idealized tracers with constant lifetimes, which are released in two different altitudes at the surface and in the stratosphere, respectively. Model resolutions from T21L19 to T106L31 were tested by performing multi-annual simulations with prescribed sea surface temperatures and sea ice fields of the 1990s. The impacts of the tracer lifetime were investigated by varying the globally uniform exponential decay time between 0.5 and 50 months. We also tested the influence of using prescribed meteorological fields (ERA40) instead of climatological sea surface temperature and sea ice fields. Meridional transport of surface tracers decreases in the coarse resolution model due to enhanced vertical mixing, with the exception of the advection into the tropical region, which shows an inconsistent trend between the resolutions. Whereas, the meridional transport of tracers released in the stratosphere was enhanced with higher model resolutions, except in the transport from tropical stratosphere to the Southern Hemisphere, which exhibits an increase trend with increasing model resolution. The idealized tracers exhibit a seasonal cycle, which is modulated by the tracer lifetime. In comparison to the run with prescribed sea surface temperature and sea ice fields, the simulation with prescribed meteorological fields did not exhibit significant change in the meridional transport, except in the exchange of stratospheric tracers between both hemispheres, where it causes about 100% increase. The import of the surface tracers into the stratosphere is increased by up to a factor of 2.5, and the export from the stratosphere into the troposphere was increased by up to 60% when prescribed meteorological fields is used. The ERA40 simulation also showed larger interannual variability (up to 24% compared to 12% in the standard simulations). Using our surface tracers released in either the northern or Southern Hemisphere, respectively, we calculate inter-hemispheric transport times between 11 and 17 months, consistent with values reported in the literature. While this study cannot be used to relate differences in model results to specific changes in transport processes, it nevertheless provides some insight into the characteristics of tracer transport in the widely used ECHAM5 general circulation model.
Hydrochlorofluorocarbon and hydrofluorocarbon emissions in East Asia determined by inverse modeling
Authors: Stohl A. , Kim J. , Li S. , O'Doherty S. , Mühle J. , Salameh P. K. , Saito T. , Vollmer M. K. , Wan D. , Weiss R. F. , Yao B. , Yokouchi Y. , Zhou L. X.
Published: April 2010

Abstract. The emissions of three hydrochlorofluorocarbons, HCFC-22 (CHClF2), HCFC-141b (CH3CCl2F) and HCFC-142b (CH3CClF2) and three hydrofluorocarbons, HFC-23 (CHF3), HFC-134a (CH2FCF3) and HFC-152a (CH3CHF2) from four East Asian countries and the Taiwan region for the year 2008 are determined by inverse modeling. The inverse modeling is based on in-situ measurements of these halocarbons at the Japanese stations Cape Ochi-ishi and Hateruma, the Chinese station Shangdianzi and the South Korean station Gosan. For every station and every 3 h, 20-day backward calculations were made with the Lagrangian particle dispersion model FLEXPART. The model output, the measurement data, bottom-up emission information and corresponding uncertainties were fed into an inversion algorithm to determine the regional emission fluxes. The model captures the observed variation of halocarbon mixing ratios very well for the two Japanese stations but has difficulties explaining the large observed variability at Shangdianzi, which is partly caused by small-scale transport from Beijing that is not adequately captured by the model. Based on HFC-23 measurements, the inversion algorithm could successfully identify the locations of factories known to produce HCFC-22 and emit HFC-23 as an unintentional byproduct. This lends substantial credibility to the inversion method. We report national emissions for China, North Korea, South Korea and Japan, as well as emissions for the Taiwan region. Halocarbon emissions in China are much larger than the emissions in the other countries together and contribute a substantial fraction to the global emissions. Our estimates of Chinese emissions for the year 2008 are 65.3±6.6 kt/yr for HCFC-22 (17% of global emissions extrapolated from Montzka et al., 2009), 12.1±1.6 kt/yr for HCFC-141b (22%), 7.3±0.7 kt/yr for HCFC-142b (17%), 6.2±0.7 kt/yr for HFC-23 (>50%), 12.9±1.7 kt/yr for HFC-134a (9% of global emissions estimated from Velders et al., 2009) and 3.4±0.5 kt/yr for HFC-152a (7%).
A new ENSO index derived from satellite measurements of column ozone
Authors: Ziemke J. R. , Chandra S. , Oman L. D. , Bhartia P. K.
Published: April 2010

Abstract. Column Ozone measured in tropical latitudes from Nimbus 7 total ozone mapping spectrometer (TOMS), Earth Probe TOMS, solar backscatter ultraviolet (SBUV), and Aura ozone monitoring instrument (OMI) are used to derive an El Nino-Southern Oscillation (ENSO) index. This index, which covers a time period from 1979 to the present, is defined as the "Ozone ENSO Index" (OEI) and is the first developed from atmospheric trace gas measurements. The OEI is constructed by first averaging monthly mean column ozone over two broad regions in the western and eastern Pacific and then taking their difference. This differencing yields a self-calibrating ENSO index which is independent of individual instrument calibration offsets and drifts in measurements over the long record. The combined Aura OMI and MLS ozone data confirm that zonal variability in total column ozone in the tropics caused by ENSO events lies almost entirely in the troposphere. As a result, the OEI can be derived directly from total column ozone instead of tropospheric column ozone. For clear-sky ozone measurements a +1 K change in Nino 3.4 index corresponds to +2.9 Dobson Unit (DU) change in the OEI, while a +1 hPa change in SOI coincides with a −1.7 DU change in the OEI. For ozone measurements under all cloud conditions these numbers are +2.4 DU and −1.4 DU, respectively. As an ENSO index based upon ozone, it is potentially useful in evaluating climate models predicting long term changes in ozone and other trace gases.
Towards closing the gap between hygroscopic growth and CCN activation for secondary organic aerosols – Part 3: Influence of the chemical composition on the hygroscopic properties and volatile fractions of aerosols
Authors: Poulain L. , Wu Z. , Petters M. D. , Wex H. , Hallbauer E. , Wehner B. , Massling A. , Kreidenweis S. M. , Stratmann F.
Published: April 2010

Abstract. The influence of varying levels of water mixing ratio, r, during the formation of secondary organic aerosol (SOA) from the ozonolysis of α-pinene on the SOA hygroscopicity and volatility was investigated. The reaction proceeded and aerosols were generated in a mixing chamber and the hygroscopic characteristics of the SOA were determined with the Leipzig Aerosol Cloud Interaction Simulator (LACIS) and a Cloud Condensation Nuclei counter (CCNc). In parallel, a High-Resolution Time-of-Flight Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS) located downstream of a thermodenuder (TD) sampling from the mixing chamber, to collect mass spectra of particles from the volatile and less-volatile fractions of the SOA. Results showed that both hygroscopic growth and the volatile fraction of the SOA increased with increases in r inside the mixing chamber during SOA generation. An effective density of 1.40 g cm−3 was observed for the generated SOA when the reaction proceeded with r>1 g kg−1. Changes in the concentrations of the fragment CO2+ and the sum of CxHyOz+ (short name CHO) and CxHy+ (short name CH) fragments as measured by the HR-ToF-AMS were used to estimate changes in the oxidation level of the SOA with reaction conditions, using the ratios CO2+ to CH and CHO to CH. Under humid conditions, both ratios increased, corresponding to the presence of more oxygenated functional groups (i.e., multifunctional carboxylic acids). This result is consistent with the α-pinene ozonolysis mechanisms which suggest that water interacts with the stabilized Criegee intermediate. The volatility and the hygroscopicity results show that SOA generation via ozonolysis of α-pinene in the presence of water vapour (r<16.9 g kg−1) leads to the formation of more highly oxygenated compounds that are more hygroscopic and more volatile than compounds formed under dry conditions.
Data assimilation of CALIPSO aerosol observations
Authors: Sekiyama T. T. , Tanaka T. Y. , Shimizu A. , Miyoshi T.
Published: April 2010

Abstract. We have developed an advanced data assimilation system for a global aerosol model with a four-dimensional ensemble Kalman filter in which the Level 1B data from the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) were successfully assimilated for the first time, to the best of the authors' knowledge. A one-month data assimilation cycle experiment for dust, sulfate, and sea-salt aerosols was performed in May 2007. The results were validated via two independent observations: 1) the ground-based lidar network in East Asia, managed by the National Institute for Environmental Studies of Japan, and 2) weather reports of aeolian dust events in Japan. Detailed four-dimensional structures of aerosol outflows from source regions over oceans and continents for various particle types and sizes were well reproduced. The intensity of dust emission at each grid point was also corrected by this data assimilation system. These results are valuable for the comprehensive analysis of aerosol behavior as well as aerosol forecasting.
Technical Note: Using a high finesse optical resonator to provide a long light path for differential optical absorption spectroscopy: CE-DOAS
Authors: Meinen J. , Thieser J. , Platt U. , Leisner T.
Published: April 2010

Abstract. Cavity enhanced methods in absorption spectroscopy have seen a considerable increase in popularity during the past decade. Especially Cavity Enhanced Absorption Spectroscopy (CEAS) established itself in atmospheric trace gas detection by providing tens of kilometers of effective light path length using a cavity as short as 1 m. In this paper we report on the construction and testing of a compact and power efficient light emitting diode based broadband Cavity Enhanced Differential Optical Absorption Spectrometer (CE-DOAS) for in situ observation of atmospheric NO3. This device combines the small size of the cavity with the advantages of the DOAS approach in terms of sensitivity, specificity and insensivity to intensity fluctuations of the light source. In particular, no selective removal of the analyte (here NO3) is necessary for calibration of the instrument if appropriate corrections are applied to the CEAS theory. Therefore the CE-DOAS technique can – in principle – measure any gas detectable by DOAS. We will discuss the advantages of using a light emitting diode (LED) as light source particularly the precautions which have to be considered for the use of LEDs with a broad wavelength range. The instrument was tested in the lab by detecting NO3 formed by mixing of NO2 and O3 in air. It was then compared to other trace gas detection techniques in an intercomparison campaign in the atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich at NO3 concentrations as low as 6.3 ppt.
Increasing synoptic scale variability in atmospheric CO2 at Hateruma Island associated with increasing East-Asian emissions
Authors: Tohjima Y. , Mukai H. , Hashimoto S. , Patra P. K.
Published: April 2010

Abstract. In-situ observations of atmospheric CO2 and CH4 at Hateruma Island (24.05° N, 123.80° E, 47 m a.s.l), Japan shows large synoptic scale variations during a 6-month period from November to April, when the sampled air is predominantly of continental origin due to the Asian winter monsoon. Synoptic scale variations are extracted from the daily averaged values for the years between 1996 and 2007, along with the annual standard deviations (σCO2 and σCH4 for CO2 and CH4, respectively) for the relevant 6-month period. During this 6-month period the absolute mixing ratios of CO2 and CH4 at Hateruma are also elevated compared to those at two sites in the central North Pacific Ocean. The temporal change in σCO2 shows a systematic increase over the 12-year period, with elevated excursions in 1998 and 2003; there is no clear increase in σCH4. We also find that the σCO2/σCH4 ratio increases gradually from 1996 to 2002 and rapidly after 2002 without any extreme deviations that characterised σCO2. The σCO2/σCH4 ratio correlates closely with the recent rapid increase in fossil carbon emissions from China, as indicated in the Carbon Dioxide Information Analysis Center (CDIAC) database. This methodology can be applied to multiple chemical tracers of sufficient lifetime, for tracking overall changes in regional emissions.
Kinetics and mechanisms of heterogeneous reaction of NO2 on CaCO3 surfaces under dry and wet conditions
Authors: Li H. J. , Zhu T. , Zhao D. F. , Zhang Z. F. , Chen Z. M.
Published: April 2010

Abstract. With increasing NO2 concentration in the troposphere, the importance of NO2 reaction with mineral dust in the atmosphere needs to be evaluated. Until now, little is known about the reaction of NO2 with CaCO3. In this study, the heterogeneous reaction of NO2 on the surface of CaCO3 particles was investigated at 296 K and NO2 concentrations between 4.58×1015 molecules cm−3 to 1.68×1016 molecules cm−3, using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) combined with X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), under wet and dry conditions. Nitrate formation was observed under both conditions, while nitrite was observed under wet conditions, indicating the reaction of NO2 on the CaCO3 surface produced nitrate and probably nitrous acid (HONO). Relative humidity (RH) influences both the initial uptake coefficient and the reaction mechanism. At low RH, surface −OH is formed through dissociation of the surface adsorbed water via oxygen vacancy, thus determining the reaction order. As RH increases, water starts to condense on the surface and the gas-liquid reaction of NO2 with the condensed water begins. With high enough RH (>52% in our experiment), the gas-liquid reaction of NO2 with condensed water becomes dominant, forming HNO3 and HONO. The initial uptake coefficient γ0 was determined to be (4.25±1.18)×10−9 under dry conditions and up to (6.56±0.34)×10−8 under wet conditions. These results suggest that the reaction of NO2 on CaCO3 particle is unable to compete with that of HNO3 in the atmosphere. Further studies at lower NO2 concentrations and with a more accurate assessment of the surface area for calculating the uptake coefficient of the reaction of NO2 on CaCO3 particle and to examine its importance as a source of HONO in the atmosphere are needed.
Fluxes and concentrations of volatile organic compounds above central London, UK
Authors: Langford B. , Nemitz E. , House E. , Phillips G. J. , Famulari D. , Davison B. , Hopkins J. R. , Lewis A. C. , Hewitt C. N.
Published: April 2010

Abstract. Concentrations and fluxes of eight volatile organic compounds (VOCs) were measured during October 2006 from a high telecom tower above central London, as part of the CityFlux contribution to the REPARTEE I campaign. A continuous flow disjunct eddy covariance technique with analysis by proton transfer reaction mass spectrometry was used. Daily averaged VOC mixing ratios were within the range 1–19 ppb for the oxygenated compounds (methanol, acetaldehyde and acetone) and 0.2–1.3 ppb for the aromatics (benzene, toluene and C2-benzenes). Typical VOC fluxes were in the range 0.1–1.0 mg m−2 h−1. There was a non-linear relationship between VOC fluxes and traffic density for most of the measured compounds. Traffic activity was estimated to account for approximately 70% of the aromatic compound fluxes, whereas non-traffic related sources were found to be more important for methanol and isoprene fluxes. The measured fluxes were comparable to the estimates of the UK national atmospheric emission inventory for the aromatic VOCs and CO. In contrast, fluxes of the oxygenated compounds were about three times larger than inventory estimates. For isoprene and acetonitrile this difference was many times larger. At temperatures over 25° C it is estimated that more than half the isoprene observed in central London is of biogenic origin.
Source identification of short-lived air pollutants in the Arctic using statistical analysis of measurement data and particle dispersion model output
Authors: Hirdman D. , Sodemann H. , Eckhardt S. , Burkhart J. F. , Jefferson A. , Mefford T. , Quinn P. K. , Sharma S. , Ström J. , Stohl A.
Published: April 2010

Abstract. As a part of the IPY project POLARCAT (Polar Study using Aircraft, Remote Sensing, Surface Measurements and Models, of Climate Chemistry, Aerosols and Transport), this paper studies the sources of equivalent black carbon (EBC), sulphate, light-scattering aerosols and ozone measured at the Arctic stations Zeppelin, Alert, Barrow and Summit during the years 2000–2007. These species are important pollutants and climate forcing agents, and sulphate and EBC are main components of Arctic haze. To determine where these substances originate, the measurement data were combined with calculations using FLEXPART, a Lagrangian particle dispersion model. The climatology of atmospheric transport from surrounding regions on a twenty-day time scale modelled by FLEXPART shows that the stations Zeppelin, Alert and Barrow are highly sensitive to surface emissions in the Arctic and to emissions in high-latitude Eurasia in winter. Emission sensitivities over southern Asia and southern North America are small throughout the year. The high-altitude station Summit is an order of magnitude less sensitive to surface emissions in the Arctic whereas emissions in the southern parts of the Northern Hemisphere continents are more influential relative to the other stations. Our results show that for EBC and sulphate measured at Zeppelin, Alert and Barrow, northern Eurasia is the dominant source region. For sulphate, Eastern Europe and the metal smelting industry in Norilsk are particularly important. For EBC, boreal forest fires also contribute in summer. No evidence for any substantial contribution to EBC from sources in southern Asia is found. European air masses are associated with low ozone concentrations in winter due to titration by nitric oxides, but are associated with high ozone concentrations in summer due to photochemical ozone formation. There is also a strong influence of ozone depletion events in the Arctic boundary layer on measured ozone concentrations in spring and summer. These results will be useful for developing emission reduction strategies for the Arctic.
Planetary wave activity in the polar lower stratosphere
Authors: Alexander S. P. , Shepherd M. G.
Published: April 2010

Abstract. Temperature data from the COSMIC GPS-RO satellite constellation are used to study the distribution and variability of planetary wave activity in the low to mid- stratosphere (15–40 km) of the Arctic and Antarctic from September 2006 until March 2009. Stationary waves are separated from travelling waves and their amplitudes, periods and small-scale vertical distribution then examined. COSMIC observed short lived (less than two weeks and less than 5 km vertically) but large enhancements in planetary wave amplitudes occurring regularly throughout all winters in both hemispheres. In contrast to recent Arctic winters, eastward wave activity during 2008–2009 was significantly reduced during the early part of the winter and immediately prior to the major SSW. The eastward waves which did exist had similar periods to the two preceding winters (~16–20 days). A westward wave with zonal wavenumber two, with distinct peaks at 22 km and 35 km and period around 16–24 days, as well as a stationary wave two were associated with the 2009 major SSW. In the Southern Hemisphere, the height structure of planetary wave amplitudes also exhibited fluctuations on short time and vertical scales superimposed upon the broader seasonal cycle. Significant inter-annual variability in planetary wave amplitude and period are noticed, with the times of cessation of significant activity also varying.
Peroxyacetic acid in urban and rural atmosphere: concentration, feedback on PAN-NOxcycle and implication on radical chemistry
Authors: Zhang X. , Chen Z. M. , He S. Z. , Hua W. , Zhao Y. , Li J. L.
Published: April 2010

Abstract. Peroxyacetic acid (PAA) is one of the most important atmospheric organic peroxides, which have received increasing attention for their potential contribution to the oxidation capacity of the troposphere and the formation of secondary aerosols. We report here, for the first time, a series of data for atmospheric PAA concentrations at urban and rural sites, from five field campaigns carried out in China in summer 2006, 2007 and 2008. For these five measurements, daytime mean (08:00–20:00 LT) PAA concentrations on sunlit days were 21.4–148.0 pptv with a maximum level of ~1 ppbv. The various meteorological and chemical parameters influencing PAA concentrations were examined using Principal Factor Analysis. This statistical analysis shows that the local photochemical production was the major source of PAA, and its concentration increased with increasing temperature, solar radiation and ozone but decreased with increasing NOx (NO and NO2), CO, SO2, and relative humidity. Based on the dataset, several issues are highlighted in this study: (i) Because PAA is a product from the photochemical oxidation of some specific volatile organic compounds (VOCs) that lead to acetyl peroxy radicals, the importance of various VOCs with respect to the PAA formation is therefore ranked using the incremental reactivity method. (ii) The contribution of PAN thermal degradation to PAA formation under conditions of different NOx concentrations is estimated based on the chemical kinetics analysis. The result shows that PAN seems to play an important role in the formation of PAA when the NO/NO2 concentration ratio was less than 0.2 and PAA would correspondingly have feedback on the PAN-NOx cycle. (iii) PAA and other peroxides, such as methyl hydroperoxide (MHP) and H2O2, usually exhibited a similar asymmetric shape typically shifted to the afternoon. However, under some conditions, H2O2 diurnal cycle was out of phase with MHP and PAA. The combination of linear regression and kinetics analysis indicate that the formation and removal processes of H2O2 may be different from those of MHP and PAA. (iv) Considering that PAA is the reservior of free radicals, its fate is expected to have an effect on the free radical budget in the atmosphere. A box model based on the CBM-IV mechanism has been performed to access its influence on the radical budget. We suggest that the detailed information on PAA in the atmosphere is of importance to better understand the free radical chemistry.
The effect of Arctic sea-ice extent on the absorbed (net) solar flux at the surface, based on ISCCP-D2 cloud data for 1983–2007
Authors: Matsoukas C. , Hatzianastassiou N. , Fotiadi A. , Pavlakis K. G. , Vardavas I.
Published: April 2010

Abstract. We estimate the effect of the Arctic sea ice on the absorbed (net) solar flux using a radiative transfer model. Ice and cloud input data to the model come from satellite observations, processed by the International Satellite Cloud Climatology Project (ISCCP) and span the period July 1983–June 2007. The sea-ice effect on the solar radiation fluctuates seasonally with the solar flux and decreases interannually in synchronisation with the decreasing sea-ice extent. A disappearance of the Arctic ice cap during the sunlit period of the year would radically reduce the local albedo and cause an annually averaged 19.7 W m−2 increase in absorbed solar flux at the Arctic Ocean surface, or equivalently an annually averaged 0.55 W m−2 increase on the planetary scale. In the clear-sky scenario these numbers increase to 34.9 and 0.97 W m−2, respectively. A meltdown only in September, with all other months unaffected, increases the Arctic annually averaged solar absorption by 0.32 W m−2. We examined the net solar flux trends for the Arctic Ocean and found that the areas absorbing the solar flux more rapidly are the North Chukchi and Kara Seas, Baffin and Hudson Bays, and Davis Strait. The sensitivity of the Arctic absorbed solar flux on sea-ice extent and cloud amount was assessed. Although sea ice and cloud affect jointly the solar flux, we found little evidence of strong non-linearities.
Hydroxyl radical reactivity at the air-ice interface
Authors: Kahan T. F. , Zhao R. , Donaldson D. J.
Published: April 2010

Abstract. Hydroxyl radicals are important oxidants in the atmosphere and in natural waters. They are also expected to be important in snow and ice, but their reactivity has not been widely studied in frozen aqueous solution. We have developed a spectroscopic probe to monitor the formation and reactions of hydroxyl radicals in situ. Hydroxyl radicals are produced in aqueous solution via the photolysis of nitrite, nitrate, and hydrogen peroxide, and react rapidly with benzene to form phenol. Similar phenol formation rates were observed in aqueous solution and bulk ice. However, no reaction was observed at air-ice interfaces, or when bulk ice samples were crushed prior to photolysis to increase their surface area. We also monitored the heterogeneous reaction between benzene present at air-water and air-ice interfaces with gas-phase OH produced from HONO photolysis. Rapid phenol formation was observed on water surfaces, but no reaction was observed at the surface of ice. Under the same conditions, we observed rapid loss of the polycyclic aromatic hydrocarbon (PAH) anthracene at air-water interfaces, but no loss was observed at air-ice interfaces. Our results suggest that the reactivity of hydroxyl radicals toward aromatic organics is similar in bulk ice samples and in aqueous solution, but is significantly suppressed in the quasi-liquid layer (QLL) that exists at air-ice interfaces.
Acetaldehyde in the Alaskan subarctic snowpack
Authors: Domine F. , Houdier S. , Taillandier A.-S. , Simpson W. R.
Published: April 2010

Abstract. Acetaldehyde is a reactive intermediate in hydrocarbon oxidation. It is both emitted and taken up by snowpacks and photochemical and physical processes are probably involved. Understanding the reactivity of acetaldehyde in snow and its processes of physical and chemical exchanges requires the knowledge of its incorporation mechanism in snow crystals. We have performed a season-long study of the evolution of acetaldehyde concentrations in the subarctic snowpack near Fairbanks (65° N), central Alaska, which is subjected to a vigorous metamorphism due to persistent elevated temperature gradients in the snowpack, between 20 and 200° C m−1. The snowpack therefore almost entirely transforms into depth hoar. We have also analyzed acetaldehyde in a manipulated snowpack where temperature gradients were suppressed. Snow crystals there transformed much more slowly and their original shapes remained recognizable for months. The specific surface area of snow layers in both types of snowpacks was also measured. We deduce that acetaldehyde is not adsorbed onto the surface of snow crystals and that most of the acetaldehyde is probably not dissolved in the ice lattice of the snow crystals. We propose that most of the acetaldehyde measured is either trapped or dissolved within organic aerosol particles trapped in snow, or that acetaldehyde is formed by the hydrolysis of organic precursors contained in organic aerosols trapped in the snow, when the snow is melted for analysis. These precursors are probably aldehyde polymers formed within the aerosol particles by acid catalysis, but might also be biological molecules. In a laboratory experiment, acetaldehyde-di-n-hexyl acetal, representing a potential acetaldehyde precursor, was subjected to our analytical procedure and reacted to form acetaldehyde. This confirms our suggestion that acetaldehyde detected in snow could be produced during the melting of snow for analysis.
Secondary organic material formed by methylglyoxal in aqueous aerosol mimics
Authors: Sareen N. , Schwier A. N. , Shapiro E. L. , Mitroo D. , McNeill V. F.
Published: April 2010

Abstract. We show that methylglyoxal forms light-absorbing secondary organic material in aqueous ammonium sulfate and ammonium nitrate solutions mimicking tropospheric aerosol particles. The kinetics were characterized using UV-Vis spectrophotometry. The results suggest that the bimolecular reaction of methylglyoxal with an ammonium or hydronium ion is the rate-limiting step for the formation of light-absorbing species, with kNH4+II=5×10−6 M−1 min−1 and kH3O+II≤10−3 M−1 min−1. Evidence of aldol condensation products and oligomeric species up to 759 amu was found using chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol-CIMS). Tentative identifications of carbon-nitrogen species and a sulfur-containing compound were also made using Aerosol-CIMS. Aqueous solutions of methylglyoxal, with and without inorganic salts, exhibit significant surface tension depression. These observations add to the growing body of evidence that dicarbonyl compounds may form secondary organic material in the aerosol aqueous phase, and that secondary organic aerosol formation via heterogeneous processes may affect seed aerosol properties.
Accommodation coefficient of HOBr on deliquescent sodium bromide aerosol particles
Authors: Wachsmuth M. , Gäggeler H. W. , von Glasow R. , Ammann M.
Published: April 2010

Abstract. Uptake of HOBr on sea salt aerosol, sea salt brine or ice is believed to be a key process providing a source of photolabile bromine (Br2) and sustaining ozone depletion cycles in the Arctic troposphere. In the present study, uptake of HOBr on sodium bromide (NaBr) aerosol particles was investigated at an extremely low HOBr concentration of 300 cm-3 using the short-lived radioactive isotopes 83-86Br. Under these conditions, at maximum one HOBr molecule was taken up per particle. The rate of uptake was clearly limited by the mass accommodation coefficient, which was calculated to be 0.6 ± 0.2. This value is a factor of 10 larger than estimates used in earlier models. The atmospheric implications are discussed using the box model "MOCCA'', showing that the increase of the accommodation coefficient of HOBr by a factor of 10 only slightly affects net ozone loss, but significantly increases chlorine release.
The UV-visible absorption cross-sections of IONO2
Authors: Mössinger J. C. , Rowley D. M. , Cox R. A.
Published: April 2010

Abstract. The UV-visible absorption spectrum of gaseous IONO2 has been measured over the wavelength range 245--415 nm using the technique of laser photolysis with time-resolved UV-visible absorption spectroscopy. IONO2 was produced in situ in the gas phase by laser flash photolysis of NO2/CF3I/N2 mixtures. Post flash spectra were deconvolved to remove contributions to the observed absorption from other reactant and product species. The resulting spectrum attributed to IONO2 consists of several overlapping broad absorption bands. Assuming a quantum yield of unity for IONO2 photolysis, model calculations show that during sunlit hours at noon, 53° N, the first order solar photolysis rate coefficient (J value) for IONO2 is 4.0 x 10-2 s-1.
Analysis of a summer smog episode in the Berlin-Brandenburg region with a nested atmosphere -- chemistry model
Authors: Bauer S. E. , Langmann B.
Published: April 2010

Abstract. An analysis of a pollution episode in an urban atmosphere, using a complex model system is presented. The nested atmosphere-chemistry model system simulates the atmospheric conditions during a one week measurement campaign, called FLUMOB, in July 1994 in Berlin-Brandenburg, Germany. The analysis shows that naturally emitted hydrocarbons played the dominant role in the ozone formation in the investigated area. The composition of non-methane volatile organic compounds was made up to 70--80% by biogenically emitted hydrocarbons. During the analysed case, ozone formation was sensitive to hydrocarbon concentrations so that the ozone production was limited by the availability of hydrocarbons and thus especially by the amount which was biogenically emitted. Furthermore, it is shown that the FLUMOB episode was influenced by elevated concentrations of ozone in the free troposphere. In contrast to previous analyses, the importance of ozone produced outside of Europe is emphasized. In spite of the stagnant high pressure situation which occurred during the FLUMOB episode Germany was significantly influenced by long-range transport of ozone. This transport also influenced near surface ozone concentrations.