bluuebunny/crossref_metadata_2025 huggingface dataset:
Applicability of condensation particle counters to measure atmospheric clusters
Authors: Sipilä M. , Lehtipalo K. , Kulmala M. , Petäjä T. , Junninen H. , Aalto P. P. , Manninen H. E. , Kyrö E.-M. , Asmi E. , Riipinen I. , Curtius J. , Kürten A. , Borrmann S. , O'Dowd C. D.
Published: April 2010

Abstract. This study presents an evaluation of a pulse height condensation particle counter (PH-CPC) and an expansion condensation particle counter (E-CPC) in terms of measuring ambient and laboratory-generated molecular and ion clusters. Ambient molecular cluster concentrations were measured with both instruments as they were deployed in conjunction with an ion spectrometer and other aerosol instruments in Hyytiälä, Finland at the SMEAR II station between 1 March and 30 June 2007. The observed cluster concentrations varied and ranged from some thousands to 100 000 cm−3. Both instruments showed similar (within a factor of ~5) concentrations. An average size of the detected clusters was approximately 1.8 nm. As the atmospheric measurement of sub 2-nm particles and molecular clusters is a challenging task, we conclude that most likely we were unable to detect the smallest clusters. Nevertheless, the reported concentrations are the best estimates to date for minimum cluster concentrations in a boreal forest environment.
Measurement and interpretation of gas phase formaldehyde concentrations obtained during the CHABLIS campaign in coastal Antarctica
Authors: Salmon R. A. , Bauguitte S. J.-B. , Bloss W. , Hutterli M. A. , Jones A. E. , Read K. , Wolff E. W.
Published: April 2010

Abstract. Gas phase formaldehyde concentrations were measured during the 2004–2005 CHABLIS campaign at Halley research station, Antarctica. Data coverage span from May 2004 through to January 2005, thus capturing the majority of the year, with a wintertime minimum of near or below the instrumental detection limit rising to between 50 and 200 pptv during the austral summer. Factors controlling HCHO concentration include local chemical sources and sinks, and exchange with the snow surface. The measured seasonality is in line with previous observations from Neumayer station, with maximum in summer and minimum during the winter months, but with lower absolute concentrations throughout the year. The gas-phase production of HCHO was dominated by methane oxidation and a steady-state analysis showed that reactions of iodine and bromine species substantially reduced the predicted HCHO levels based upon in situ chemistry. This indicates a substantial additional HCHO source to be present that could be explained by a snowpack source.
Depletion of gaseous polycyclic aromatic hydrocarbons by a forest canopy
Authors: Choi S.-D. , Staebler R. M. , Li H. , Su Y. , Gevao B. , Harner T. , Wania F.
Published: April 2010

Abstract. Rapid uptake of gaseous polycyclic aromatic hydrocarbons (PAHs) by a forest canopy was observed at Borden in Southern Ontario, Canada during bud break in early spring 2003. High volume air samples were taken on 12 individual days at three different heights (44.4, 29.1, and 16.7 m) on a scaffolding tower and on the forest floor below the canopy (1.5 m). Concentrations of PAHs were positively correlated to ambient temperature, resulting from relatively warm and polluted air masses passing over the Eastern United States and Toronto prior to arriving at the sampling site. An analysis of vertical profiles and gas/particle partitioning of the PAHs showed that gaseous PAHs established a concentration gradient with height, whereas levels of particulate PAHs were relatively uniform, implying that only the uptake of gaseous PAHs by the forest canopy was sufficiently rapid to be observed. Specifically, the gaseous concentrations of intermediate PAHs, such as phenanthrene, anthracene, and pyrene, during budburst and leaf emergence were reduced within and above the canopy. When a gradient was observed, the percentage of PAHs on particles increased at the elevations experiencing a decrease in gas phase concentrations. The uptake of intermediate PAHs by the canopy also led to significant differences in gaseous PAH composition with height. These results are the most direct evidence yet of the filter effect of forest canopies for gaseous PAHs in early spring. PAH deposition fluxes and dry gaseous deposition velocities to the forest canopy were estimated from the concentration gradients.
Changes in aerosol properties during spring-summer period in the Arctic troposphere
Authors: Engvall A.-C. , Krejci R. , Ström J. , Treffeisen R. , Scheele R. , Hermansen O. , Paatero J.
Published: April 2010

Abstract. The change in aerosol properties during the transition from the more polluted spring to the clean summer in the Arctic troposphere was studied. A six-year data set of observations from Ny-Ålesund on Svalbard, covering the months April through June, serve as the basis for the characterisation of this time period. In addition four-day-back trajectories were used to describe air mass histories. The observed transition in aerosol properties from an accumulation-mode dominated distribution to an Aitken-mode dominated distribution is discussed with respect to long-range transport and influences from natural and anthropogenic sources of aerosols and pertinent trace gases. Our study shows that the air-mass transport is an important factor modulating the physical and chemical properties observed. However, the air-mass transport cannot alone explain the annually repeated systematic and rather rapid change in aerosol properties, occurring within a limited time window of approximately 10 days. With a simplified phenomenological model, which delivers the nucleation potential for new-particle formation, we suggest that the rapid shift in aerosol microphysical properties between the Arctic spring and summer is mainly driven by the incoming solar radiation in concert with transport of precursor gases and changes in condensational sink.
Improved simulation of isoprene oxidation chemistry with the ECHAM5/MESSy chemistry-climate model: lessons from the GABRIEL airborne field campaign
Authors: Butler T. M. , Taraborrelli D. , Brühl C. , Fischer H. , Harder H. , Martinez M. , Williams J. , Lawrence M. G. , Lelieveld J.
Published: April 2010

Abstract. The GABRIEL airborne field measurement campaign, conducted over the Guyanas in October 2005, produced measurements of hydroxyl radical (OH) concentration which are significantly higher than can be simulated using current generation models of atmospheric chemistry. Based on the hypothesis that this "missing OH" is due to an as-yet undiscovered mechanism for recycling OH during the oxidation chain of isoprene, we determine that an OH recycling of about 40–50% (compared with 5–10% in current generation isoprene oxidation mechanisms) is necessary in order for our modelled OH to approach the lower error bounds of the OH observed during GABRIEL. Such a large amount of OH in our model leads to unrealistically low mixing ratios of isoprene. In order for our modelled isoprene mixing ratios to match those observed during the campaign, we also require that the effective rate constant for the reaction of isoprene with OH be reduced by about 50% compared with the lower bound of the range recommended by IUPAC. We show that a reasonable explanation for this lower effective rate constant could be the segregation of isoprene and OH in the mixed layer. Our modelling results are consistent with a global, annual isoprene source of about 500 Tg(C) yr−1, allowing experimentally derived and established isoprene flux rates to be reconciled with global models.
Validation of UV-visible aerosol optical thickness retrieved from spectroradiometer measurements
Authors: Brogniez C. , Buchard V. , Auriol F.
Published: April 2010

Abstract. Global and diffuse UV-visible solar irradiances are routinely measured since 2003 with a spectroradiometer operated by the Laboratoire d'Optique Atmosphérique (LOA) located in Villeneuve d'Ascq, France. The analysis of the direct irradiance derived by cloudless conditions enables retrieving the aerosol optical thickness (AOT) spectrum in the 330–450 nm range. The site hosts also sunphotometers from the AERONET/PHOTONS network performing routinely measurements of the AOT at several wavelengths. On one hand, comparisons between the spectroradiometer and the sunphotometer AOT at 440 nm as well as, when available, at 340 and 380 nm, show good agreement: in 2003–2005 at 440 nm the correlation coefficient, the slope and the intercept of the regression line are [0.97, 0.95, 0.025], and in 2006 at 440, 380 and 340 nm they are [0.97, 1.00, −0.013], [0.97, 0.98, −0.007], and [0.98, 0.98, −0.002] respectively. On the other hand, the AOT's spectral variations have been compared using the Angström exponents derived from AOT data at 340 and 440 nm for both instruments. The comparisons show that this parameter is difficult to retrieve accurately due to the small wavelength range and due to the weak AOT values. Thus, AOT derived at wavelengths outside the spectroradiometer range by means of an extrapolation using the Angström parameter would have large uncertainties, whereas spectroradiometer's spectral AOT could be used for direct validation of other AOT, such as those provided by satellite instruments.
Eclipse effects on field crops and marine zooplankton: the 29 March 2006 total solar eclipse
Authors: Economou G. , Christou E. D. , Giannakourou A. , Gerasopoulos E. , Georgopoulos D. , Kotoulas V. , Lyra D. , Tsakalis N. , Tzortziou M. , Vahamidis P. , Papathanassiou E. , Karamanos A.
Published: April 2010

Abstract. Some effects in the biosphere from the Total Solar Eclipse of 29 March 2006 were investigated in field crops and marine zooplankton. Taking into account the decisive role of light on plant life and productivity, measurements of photosynthesis and stomatal behaviour were conducted on seven important field-grown cereal and leguminous crops. A drop in photosynthetic rates, by more than a factor of 5 in some cases, was observed, and the minimum values of photosynthetic rates ranged between 3.13 and 10.13 μmol CO2 m−2 s−1. The drop in solar irradiance and the increase in mesophyll CO2-concentration during the eclipse did not induce stomatal closure thus not blocking CO2 uptake by plants. Light effects on the photochemical phase of photosynthesis may be responsible for the observed depression in photosynthetic rates. Field studies addressing the migratory responses of marine zooplankton (micro-zooplankton (ciliates), and meso-zooplankton) due to the rapid changes in underwater light intensity were also performed. The light intensity attenuation was simulated with the use of accurate underwater radiative transfer modeling techniques. Ciliates, responded to the rapid decrease in light intensity during the eclipse adopting night-time behaviour. From the meso-zooplankton assemblage, various vertical migratory behaviours were adopted by different species.
Measurement-based modeling of bromine chemistry in the Dead Sea boundary layer – Part 2: The influence of NO2 on bromine chemistry at mid-latitude areas
Authors: Tas E. , Peleg M. , Pedersen D. U. , Matveev V. , Biazar A. P. , Luria M.
Published: April 2010

Abstract. Understanding the interaction between anthropogenic air pollution and Reactive Halogen Species (RHS) activity has had only limited support from direct field measurements, due to the fact that past field measurements of RHS have been mainly performed in Polar Regions. The present paper investigates the interaction between NO2 and Reactive Bromine Species (RBS) activity by model simulations based on extensive field measurements performed in the Dead Sea area, as described in a companion paper (Tas et al., 2006). The Dead Sea is an excellent natural laboratory for this investigation since elevated mixing ratios of BrO (up to more than 150 pptv) are frequently observed, while the average levels of NO2 are around several ppb. The results of the present study show that under the chemical mechanisms that occur at the Dead Sea, higher levels of NO2 lead to higher daily average mixing ratios of BrOx. This is the result of an increase in the rate of the heterogeneous decomposition of BrONO2, which in turn causes an increase in the rate of the "Bromine Explosion" mechanism. However, above a certain threshold level of NO2 (daily average mixing ratios of 0.2 ppbv during RBS activity), the daily average mixing ratios of BrOx decrease for a further increase in the NO2 mixing ratios. This investigation shows that the influence of NO2 on BrOx production clearly reflects an enhancement of RBS activity caused by anthropogenic activity.
Analysis of global water vapour trends from satellite measurements in the visible spectral range
Authors: Mieruch S. , Noël S. , Bovensmann H. , Burrows J. P.
Published: April 2010

Abstract. Global water vapour total column amounts have been retrieved from spectral data provided by the Global Ozone Monitoring Experiment (GOME) flying on ERS-2, which was launched in April 1995, and the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) onboard ENVISAT launched in March 2002. For this purpose the Air Mass Corrected Differential Optical Absorption Spectroscopy (AMC-DOAS) approach has been used. The combination of the data from both instruments provides us with a long-term global data set spanning more than 11 years with the potential of extension up to 2020 by GOME-2 data on MetOp. Using linear and non-linear methods from time series analysis and standard statistics the trends of H2O columns and their errors have been calculated. In this study, factors affecting the trend such as the length of the time series, the magnitude of the variability of the noise, and the autocorrelation of the noise are investigated. Special emphasis has been placed on the calculation of the statistical significance of the observed trends, which reveal significant local changes from −5% per year to +5% per year. These significant trends are distributed over the whole globe. Increasing trends have been calculated for Greenland, East Europe, Siberia and Oceania, whereas decreasing trends have been observed for the northwest USA, Central America, Amazonia, Central Africa and the Arabian Peninsular.
Twelve years of global observations of formaldehyde in the troposphere using GOME and SCIAMACHY sensors
Authors: De Smedt I. , Müller J.-F. , Stavrakou T. , van der A R. , Eskes H. , Van Roozendael M.
Published: April 2010

Abstract. This work presents global tropospheric formaldehyde columns retrieved from near-UV radiance measurements performed by the GOME instrument onboard ERS-2 since 1995, and by SCIAMACHY, in operation on ENVISAT since the end of 2002. A special effort has been made to ensure the coherence and quality of the CH2O dataset covering the period 1996–2007. Optimised DOAS settings are proposed in order to reduce the impact of two important sources of error in the derivation of slant columns, namely, the polarisation anomaly affecting the SCIAMACHY spectra around 350 nm, and a major absorption band of the O4 collision complex centred near 360 nm. The air mass factors are determined from scattering weights generated using radiative transfer calculations taking into account the cloud fraction, the cloud height and the ground albedo. Vertical profile shapes of CH2O are provided by the global CTM IMAGES based on an up-to-date representation of emissions, atmospheric transport and photochemistry. A comprehensive error analysis is presented. This includes errors on the slant columns retrieval and errors on the air mass factors which are mainly due to uncertainties in the a priori profile and in the cloud properties. The major features of the retrieved formaldehyde column distribution are discussed and compared with previous CH2O datasets over the major emission regions.
Pressure broadening in the 2ν3 band of methane and its implication on atmospheric retrievals
Authors: Frankenberg C. , Warneke T. , Butz A. , Aben I. , Hase F. , Spietz P. , Brown L. R.
Published: April 2010

Abstract. N2-broadened half widths and pressure shifts were obtained for transitions in the 2ν3 methane band. Laboratory measurements recorded at 0.011 cm−1 resolution with a Bruker 120 HR Fouriertransform spectrometer were analysed from 5860 to 6185 cm−1. A 140 cm gas cell was filled with methane at room temperature and N2 as foreign gas at pressures ranging from 125 to 900 hPa. A multispectrum nonlinear constrained least squares approach based on Optimal Estimation was applied to derive the spectroscopic parameters by simultaneously fitting laboratory spectra at different ambient pressures assuming a Voigt line-shape. At room temperature, the half widths ranged between 0.030 and 0.071 cm−1 atm−1, and the pressure shifts varied from –0.002 to –0.025 cm−1 atm−1 for transitions up to J"=10. Especially for higher rotational levels, we find systematically narrower lines than HITRAN predicts. The Q and R branch of the new set of spectroscopic parameters is further tested with ground based direct sun Fourier transform infrared (FTIR) measurements where systematic fit residuals reduce by about a factor of 3–4. We report the implication of those differences on atmospheric methane measurements using high-resolution ground based FTIR measurements as well as low-resolution spectra from the SCanning Imaging Absorption SpectroMeter for Atmospheric ChartographY (SCIAMACHY) instrument onboard ENVISAT. We find that for SCIAMACHY, a latitudinal and seasonally varying bias of about 1% can be introduced by erroneous broadening parameters.
The effect of fatty acid surfactants on the uptake of nitric acid to deliquesced NaCl aerosol
Authors: Stemmler K. , Vlasenko A. , Guimbaud C. , Ammann M.
Published: April 2010

Abstract. Surface active organic compounds have been observed in marine boundary layer aerosol. Here, we investigate the effect such surfactants have on the uptake of nitric acid (HNO3), an important removal reaction of nitrogen oxides in the marine boundary layer. The uptake of gaseous HNO3 on deliquesced NaCl aerosol was measured in a flow reactor using HNO3 labelled with the short-lived radioactive isotope 13N. The uptake coefficient γ on pure deliquesced NaCl aerosol was γ=0.5±0.2 at 60% relative humidity and 30 ppb HNO3(g). The uptake coefficient was reduced by a factor of 5–50 when the aerosol was coated with saturated linear fatty acids with carbon chain lengths of 18 and 15 atoms in monolayer quantities. In contrast, neither shorter saturated linear fatty acids with 12 and 9 carbon atoms, nor coatings with the unsaturated oleic acid (C18, cis-double bond) had a detectable effect on the rate of HNO3 uptake. It is concluded that it is the structure of the monolayers formed, which determines their resistance towards HNO3 uptake. Fatty acids (C18 and C15), which form a highly ordered film in the so-called liquid condensed state, represent a significant barrier towards HNO3 uptake, while monolayers of shorter-chain fatty acids (C9, C12) and of the unsaturated oleic acid form a less ordered film in the liquid expanded state and do not hinder the uptake. Similarly, high contents of humic acids in the aerosol, a structurally inhomogeneous, quite water soluble mixture of oxidised high molecular weight organic compounds did not affect HNO3 uptake. As surfactant films on naturally occurring aerosol are expected to be less structured due to their chemical inhomogeneity, it is likely that their inhibitory effect on HNO3 uptake is smaller than that observed here for the C15 and C18 fatty acid monolayers.
Do atmospheric aerosols form glasses?
Authors: Zobrist B. , Marcolli C. , Pedernera D. A. , Koop T.
Published: April 2010

Abstract. A new process is presented by which water soluble organics might influence ice nucleation, ice growth, chemical reactions and water uptake of aerosols in the upper troposphere: the formation of glassy aerosol particles. Glasses are disordered amorphous (non-crystalline) solids that form when a liquid is cooled without crystallization until the viscosity increases exponentially and molecular diffusion practically ceases. The glass transition temperatures, Tg, homogeneous ice nucleation temperatures, Thom, and ice melting temperatures, Tm, of various aqueous inorganic, organic and multi-component solutions are investigated with a differential scanning calorimeter. The investigated solutes are: various polyols, glucose, raffinose, levoglucosan, an aromatic compound, sulfuric acid, ammonium bisulfate and mixtures of dicarboxylic acids (M5), of dicarboxylic acids and ammonium sulfate (M5AS), of two polyols, of glucose and ammonium nitrate, and of raffinose and M5AS. The results indicate that aqueous solutions of the investigated inorganic solutes show Tg values that are too low to be of atmospheric importance. In contrast, aqueous organic and multi-component solutions readily form glasses at low but atmospherically relevant temperatures (≤230 K). To apply the laboratory data to the atmospheric situation, the measured phase transition temperatures were transformed from a concentration to a water activity scale by extrapolating water activities determined between 252 K and 313 K to lower temperatures. The obtained state diagrams reveal that the higher the molar mass of the aqueous organic or multi-component solutes, the higher Tg of their respective solutions at a given water activity. To a lesser extent, Tg also depends on the hydrophilicity of the organic solutes. Therefore, aerosol particles containing larger (≳150 g mol−1) and more hydrophobic organic molecules are more likely to form glasses at intermediate to high relative humidities in the upper troposphere. Our results suggest that the water uptake of aerosols, heterogeneous chemical reactions in aerosol particles, as well as ice nucleation and ice crystal growth can be significantly impeded or even completely inhibited in organic-enriched aerosols at upper tropospheric temperatures with implications for cirrus cloud formation and upper tropospheric relative humidity.
First airborne water vapor lidar measurements in the tropical upper troposphere and mid-latitudes lower stratosphere: accuracy evaluation and intercomparisons with other instruments
Authors: Kiemle C. , Wirth M. , Fix A. , Ehret G. , Schumann U. , Gardiner T. , Schiller C. , Sitnikov N. , Stiller G.
Published: April 2010

Abstract. In the tropics, deep convection is the major source of uncertainty in water vapor transport to the upper troposphere and into the stratosphere. Although accurate measurements in this region would be of first order importance to better understand the processes that govern stratospheric water vapor concentrations and trends in the context of a changing climate, they are sparse because of instrumental shortcomings and observational challenges. Therefore, the Falcon research aircraft of the Deutsches Zentrum für Luft- und Raumfahrt (DLR) flew a zenith-viewing water vapor differential absorption lidar (DIAL) during the Tropical Convection, Cirrus and Nitrogen Oxides Experiment (TROCCINOX) in 2004 and 2005 in Brazil. The measurements were performed alternatively on three water vapor absorption lines of different strength around 940 nm. These are the first aircraft DIAL measurements in the tropical upper troposphere and in the mid-latitudes lower stratosphere. Sensitivity analyses reveal an accuracy of 5% between altitudes of 8 and 16 km. This is confirmed by intercomparisons with the Fast In-situ Stratospheric Hygrometer (FISH) and the Fluorescent Advanced Stratospheric Hygrometer (FLASH) onboard the Russian M-55 Geophysica research aircraft during five coordinated flights. The average relative differences between FISH and DIAL amount to −3%±8% and between FLASH and DIAL to −8%±14%, negative meaning DIAL is more humid. The average distance between the probed air masses was 129 km. The DIAL is found to have no altitude- or latitude-dependent bias. A comparison with the balloon ascent of a laser absorption spectrometer gives an average difference of 0%±19% at a distance of 75 km. Six tropical DIAL under-flights of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on board ENVISAT reveal a mean difference of −8%±49% at an average distance of 315 km. While the comparison with MIPAS is somewhat less significant due to poorer comparison conditions, the agreement with the in-situ hygrometers provides evidence of the excellent quality of FISH, FLASH and DIAL. Most DIAL profiles exhibit a smooth exponential decrease of water vapor mixing ratio in the tropical upper troposphere to lower stratosphere transition. The hygropause with a minimum mixing ratio of 2.5 µmol/mol is found between 15 and 17 km. A high-resolution (2 km horizontal, 0.2 km vertical) DIAL cross section through the anvil outflow of tropical convection shows that the ambient humidity is increased by a factor of three across 100 km.
Parameterization of N2O5reaction probabilities on the surface of particles containing ammonium, sulfate, and nitrate
Authors: Davis J. M. , Bhave P. V. , Foley K. M.
Published: April 2010

Abstract. A parameterization was developed for the heterogeneous reaction probability (γ) of N2O5 as a function of temperature, relative humidity (RH), particle composition, and phase state, for use in advanced air quality models. The reaction probabilities on aqueous NH4HSO4, (NH4)2SO4, and NH4NO3 were modeled statistically using data and uncertainty values compiled from seven different laboratory studies. A separate regression model was fit to laboratory data for dry NH4HSO4 and (NH4)2SO4 particles, yielding lower γ values than the corresponding aqueous parameterizations. The regression equations reproduced 80% of the laboratory data within a factor of two and 63% within a factor of 1.5. A fixed value was selected for γ on ice-containing particles based on a review of the literature. The combined parameterization was applied under atmospheric conditions representative of the eastern United States using 3-dimensional fields of temperature, RH, sulfate, nitrate, and ammonium. The resulting spatial distributions of γ were contrasted with three other parameterizations that have been applied in air quality models in the past and with atmospheric observational determinations of γ. Our equations lay the foundation for future research that will parameterize the suppression of γ when inorganic ammoniated particles are mixed or coated with organic material. Our analyses draw attention to a major uncertainty in the available laboratory data at high RH and highlight a critical need for future laboratory measurements of γ at low temperature and high RH to improve model simulations of N2O5 hydrolysis during wintertime conditions.
Weekly patterns of México City's surface concentrations of CO, NOx, PM10and O3during 1986–2007
Authors: Stephens S. , Madronich S. , Wu F. , Olson J. B. , Ramos R. , Retama A. , Muñoz R.
Published: April 2010

Abstract. Surface pollutant concentrations in México City show a distinct pattern of weekly variations similar to that observed in many other cities of the world. Measurements of the concentrations of carbon monoxide (CO), nitrogen oxides (NOx=NO+NO2), particulate matter smaller than 10 μm (PM10), and ozone (O3) collected hourly over 22 years (1986–2007) at 39 urban monitoring locations were analyzed. Morning concentrations of CO, NOx, and PM10 are lower on Saturdays and even more so on Sundays, compared to workdays (Monday–Friday), while afternoon O3 concentrations change minimally and are occasionally even higher. This weekend effect is empirical evidence that photochemical O3 production is NOx-inhibited, and to the extent that emissions of CO are proportional to those of reactive volatile organic compounds (VOCs), it is VOC-limited, at least in the urban areas for which the monitoring stations are representative. The VOC-limitation has increased in the past decade, due to decreases in the concentrations of CO (and presumably VOCs) and consequent decreases in the CO/NOx and VOC/NOx ratios. Enhancements of photolysis frequencies resulting from smaller weekend aerosol burdens are not negligible, but fall short of being an alternate explanation for the observed weekend effect. The strength of the weekend effect indicates that local radical termination occurs primarily via formation of nitric acid and other NOx-related compounds, some of which (e.g. peroxy acyl nitrates) can contribute to the regional NOx budget. While VOC emission reductions would be most effective in reducing local O3 production, NOx emission reduction may be more important for controlling regional oxidants.
Odin/OSIRIS observations of stratospheric NO3 through sunrise and sunset
Authors: McLinden C. A. , Haley C. S.
Published: April 2010

Abstract. The nitrate radical (NO3) has been detected in visible limb-scattered spectra measured by the Optical Spectrograph and InfraRed Imager System (OSIRIS) on-board the Odin satellite when observing at large solar zenith angles (91–97°). Apparent slant column densities of NO3 at tangent heights between 10 and 45 km are derived via spectral fitting in the 610–680 nm window. Using observations from multiple scans spanning solar zenith angles of 91–97°, the rapid evolution of NO3 through sunrise and sunset can be traced. Slant column densities are found to be generally consistent with those simulated using a radiative transfer model with coupled photochemistry. In addition, a strong dependence of NO3 with temperature is observed. These results indicate that our current knowledge of NO3 photochemistry is generally consistent with OSIRIS observations to within the limitations of the radiative transfer modeling. Furthermore, they reveal that OSIRIS possesses signal-to-noise sufficient to make useful measurements of scattered sunlight out to solar zenith angles of 91–97° and suggest the possibility of retrieving profile information for NO3 and other species at large solar zenith angles.
Eddy covariance measurements of sea spray particles over the Atlantic Ocean
Authors: Norris S. J. , Brooks I. M. , de Leeuw G. , Smith M. H. , Moerman M. , Lingard J. J. N.
Published: April 2010

Abstract. Most estimates of sea spray aerosol source functions have used indirect means to infer the rate of production as a function of wind speed. Only recently has the technology become available to make high frequency measurements of aerosol spectra suitable for direct eddy correlation determination of the sea spray particle flux. This was accomplished in this study by combining a newly developed fast aerosol particle counter with an ultrasonic anemometer which allowed for eddy covariance measurements of size-segregated particle fluxes. The aerosol instrument is the Compact Lightweight Aerosol Spectrometer Probe (CLASP) – capable of measuring 8-channel size spectra for mean radii between 0.15 and 3.5 µm at 10 Hz. The first successful measurements were made during the Waves, Air Sea Fluxes, Aerosol and Bubbles (WASFAB) field campaign in October 2005 in Duck (NC, USA). The method and initial results are presented and comparisons are made with recent sea spray source functions from the literature.
A combined particle trap/HTDMA hygroscopicity study of mixed inorganic/organic aerosol particles
Authors: Zardini A. A. , Sjogren S. , Marcolli C. , Krieger U. K. , Gysel M. , Weingartner E. , Baltensperger U. , Peter T.
Published: April 2010

Abstract. Atmospheric aerosols are often mixtures of inorganic and organic material. Organics can represent a large fraction of the total aerosol mass and are comprised of water-soluble and insoluble compounds. Increasing attention was paid in the last decade to the capability of mixed inorganic/organic aerosol particles to take up water (hygroscopicity). We performed hygroscopicity measurements of internally mixed particles containing ammonium sulfate and carboxylic acids (citric, glutaric, adipic acid) in parallel with an electrodynamic balance (EDB) and a hygroscopicity tandem differential mobility analyzer (HTDMA). The organic compounds were chosen to represent three distinct physical states. During hygroscopicity cycles covering hydration and dehydration measured by the EDB and the HTDMA, pure citric acid remained always liquid, adipic acid remained always solid, while glutaric acid could be either. We show that the hygroscopicity of mixtures of the above compounds is well described by the Zdanovskii-Stokes-Robinson (ZSR) relationship as long as the two-component particle is completely liquid in the ammonium sulfate/glutaric acid system; deviations up to 10% in mass growth factor (corresponding to deviations up to 3.5% in size growth factor) are observed for the ammonium sulfate/citric acid 1:1 mixture at 80% RH. We observe even more significant discrepancies compared to what is expected from bulk thermodynamics when a solid component is present. We explain this in terms of a complex morphology resulting from the crystallization process leading to veins, pores, and grain boundaries which allow for water sorption in excess of bulk thermodynamic predictions caused by the inverse Kelvin effect on concave surfaces.
Effects of urban pollution on UV spectral irradiances
Authors: McKenzie R. L. , Weinreis C. , Johnston P. V. , Liley B. , Shiona H. , Kotkamp M. , Smale D. , Takegawa N. , Kondo Y.
Published: April 2010

Abstract. Spectral measurements of UV irradiances at Tokyo are compared with corresponding measurements at a pristine site (Lauder New Zealand) to identify the causes of the reductions in urban UV irradiances, and to quantify their effects. Tropospheric extinctions in Tokyo were found to be up to ~40% greater than at Lauder. Most of these differences can be explained by differences in cloud and aerosols, but ozone differences are also important in the summer. Examining spectral signatures of tropospheric transmission of both sites shows that reductions due to mean NO2 and SO2 amounts are generally small. However, at times the amount of NO2 can be 10 times higher than the mean amount, and on these days it can decrease the UVA irradiance up to 40%. If SO2 shows comparable day to day variability, it would contribute to significant reductions in UVB irradiances. The results indicate that at Tokyo, interactions between the larger burden of tropospheric ozone and aerosols also have a significant effect. These results have important implications for our ability to accurately retrieve surface UV irradiances at polluted sites from satellites that use backscattered UV. Supplementary data characterising these boundary layer effects are probably needed.
The role of sea-salt emissions and heterogeneous chemistry in the air quality of polluted coastal areas
Authors: Athanasopoulou E. , Tombrou M. , Pandis S. N. , Russell A. G.
Published: April 2010

Abstract. Open-ocean and surf-zone sea-salt aerosol (SSA) emission parameterizations are incorporated in the CAMx aerosol model and applied over an area with an extended Archipelago (Greece), with a fine grid nested over the highly populated Attica peninsula. The maximum indirect impact of SSA on PM10 mass (35%) is located over a marine area with moderate SSA production and elevated shipping emissions (central Aegean Sea) where SSA interacts with anthropogenic nitric acid forming sodium nitrate. SSA increases PM10 levels in the Athens city center up to 25% during stable onshore winds. Under such conditions both open-ocean and surf-zone mechanisms contribute to aerosol production over Attica. A hybrid scheme for gas-to-particle mass transfer is necessary for accurately simulating semi-volatile aerosol components when coarse SSA is included. Dynamically simulating mass transfer to the coarse particles leads to a quadrupling of predicted PM10 nitrate in the Athens city center and up to two orders of magnitude in its coarse mass in comparison to using a bulk equilibrium approach.
Contributions of pollutants from North China Plain to surface ozone at the Shangdianzi GAW Station
Authors: Lin W. , Xu X. , Zhang X. , Tang J.
Published: April 2010

Abstract. Regional ozone pollution has become one of the top environmental concerns in China, especially in those economically vibrant and densely populated regions, such as North China region including Beijing. To address this issue, surface ozone and ancillary data over the period 2004–2006 from the Shangdianzi Regional Background Station in north China were analyzed. Due to the suitable location and valley topography of the site, transport of pollutants from the North China Plain was easily observed and quantified according to surface wind directions. Regional (polluted) and background (clean) ozone concentrations were obtained by detailed statistic analysis. Contribution of pollutants from North China Plain to surface ozone at SDZ was estimated by comparing ozone concentrations observed under SW wind conditions and that under NE wind conditions. The average daily accumulated ozone contribution was estimated to be 240 ppb·hr. The average regional contributions to surface ozone at SDZ from the North China Plain were 21.8 ppb for the whole year, and 19.2, 28.9, 25.0, and 10.0 ppb for spring, summer, autumn, and winter, respectively. The strong ozone contribution in summer led to disappearance of the spring ozone maximum phenomenon at SDZ under winds other than from the NNW to E sectors. The emissions of nitrogen oxide in the North China plain cause a decrease in ozone concentrations in winter.
Rural continental aerosol properties and processes observed during the Hohenpeissenberg Aerosol Characterization Experiment (HAZE2002)
Authors: Hock N. , Schneider J. , Borrmann S. , Römpp A. , Moortgat G. , Franze T. , Schauer C. , Pöschl U. , Plass-Dülmer C. , Berresheim H.
Published: April 2010

Abstract. Detailed investigations of the chemical and microphysical properties of rural continental aerosols were performed during the HAZE2002 experiment, which was conducted in May 2002 at the Meteorological Observatory Hohenpeissenberg (DWD) in Southern Germany. Online measurements included: Size-resolved chemical composition of submicron particles; total particle number concentrations and size distributions over the diameter range of 3 nm to 9 μm; gas-phase concentration of monoterpenes, CO, O3, OH, and H2SO4. Filter sampling and offline analytical techniques were used to determine: Fine particle mass (PM2.5), organic, elemental and total carbon in PM2.5 (OC2.5, EC2.5, TC2.5), and selected organic compounds (dicarboxylic acids, polycyclic aromatic hydrocarbons, proteins). Overall, the non-refractory components of submicron particles detected by aerosol mass spectrometry (PM1, 6.6±5.4 μg m−3, arithmetic mean and standard deviation) accounted for ~62% of PM2.5 determined by filter gravimetry (10.6±4.7 μg m−3). The relative proportions of non-refractory submicron particle components were: (23±39)% ammonium nitrate, (27±23)% ammonium sulfate, and (50±40)% organics (OM1). OM1 was closely correlated with PM1 (r2=0.9) indicating a near-constant ratio of non-refractory organics and inorganics. The average ratio of OM1 to OC2.5 was 2.1±1.4, indicating a high proportion of heteroelements in the organic fraction of the sampled rural aerosol. This is consistent with the high ratio of oxygenated organic aerosol (OOA) over hydrocarbon-like organic aerosol (HOA) inferred from the AMS results (4:1), and also with the high abundance of proteins (~3%) indicating a high proportion of primary biological material (~30%) in PM2.5. This finding was confirmed by low abundance of PAHs (<1 ng m−3) and EC (<1 μg m−3) in PM2.5 and detection of several secondary organic aerosol compounds (dicarboxylic acids) and their precursors (monoterpenes). New particle formation was observed almost every day with particle number concentrations exceeding 104 cm−3 (nighttime background level 1000–2000 cm−3). Closer inspection of two major events indicated that the observed nucleation agrees with ternary H2SO4/H2O/NH3 nucleation and that condensation of both organic and inorganic species contributed to particle growth.
SO2 Retrieval from SCIAMACHY using the Weighting Function DOAS (WFDOAS) technique: comparison with Standard DOAS retrieval
Authors: Lee C. , Richter A. , Weber M. , Burrows J. P.
Published: April 2010

Abstract. Atmospheric SO2 can be measured by remote sensing of scattered sunlight from space, using its unique absorption features in the ultraviolet region. However, the sensitivity of the SO2 measurement depends critically on spectral interference, surface albedo and varies with wavelength as Rayleigh scattering increases at shorter wavelengths. The Weighting Function Differential Optical Absorption Spectroscopy (WFDOAS) method was used to pinpoint these problems and improve the retrieval. The Ring spectra included in the WFDOAS fit were determined as a function of total ozone column density, solar zenith angle, surface albedo, and effective scene altitude. The WFDOAS SO2 retrieval from SCIAMACHY (Scanning Imaging Absorption Spectrometer for Atmospheric Chartography) data onboard the ENVISAT satellite are presented here and compared to those of the Standard DOAS (SDOAS) method for cases of background conditions and volcanic eruption. The study demonstrates the problems in the SO2 retrieval with SDOAS, such as the positive offsets over remote (clean) regions and the negative offsets at high solar zenith angles and high ozone, could be attributed to imperfect correction for the varying ozone dependence of the Ring effect and could be solved by the WFDOAS approach.
Validation of ACE-FTS v2.2 measurements of HCl, HF, CCl3F and CCl2F2 using space-, balloon- and ground-based instrument observations
Authors: Mahieu E. , Duchatelet P. , Demoulin P. , Walker K. A. , Dupuy E. , Froidevaux L. , Randall C. , Catoire V. , Strong K. , Boone C. D. , Bernath P. F. , Blavier J.-F. , Blumenstock T. , Coffey M. , De Mazière M. , Griffith D. , Hannigan J. , Hase F. , Jones N. , Jucks K. W. , Kagawa A. , Kasai Y. , Mebarki Y. , Mikuteit S. , Nassar R. , Notholt J. , Rinsland C. P. , Robert C. , Schrems O. , Senten C. , Smale D. , Taylor J. , Tétard C. , Toon G. C. , Warneke T. , Wood S. W. , Zander R. , Servais C.
Published: April 2010

Abstract. Hydrogen chloride (HCl) and hydrogen fluoride (HF) are respectively the main chlorine and fluorine reservoirs in the Earth's stratosphere. Their buildup resulted from the intensive use of man-made halogenated source gases, in particular CFC-11 (CCl3F) and CFC-12 (CCl2F2), during the second half of the 20th century. It is important to continue monitoring the evolution of these source gases and reservoirs, in support of the Montreal Protocol and also indirectly of the Kyoto Protocol. The Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) is a space-based instrument that has been performing regular solar occultation measurements of over 30 atmospheric gases since early 2004. In this validation paper, the HCl, HF, CFC-11 and CFC-12 version 2.2 profile data products retrieved from ACE-FTS measurements are evaluated. Volume mixing ratio profiles have been compared to observations made from space by MLS and HALOE, and from stratospheric balloons by SPIRALE, FIRS-2 and Mark-IV. Partial columns derived from the ACE-FTS data were also compared to column measurements from ground-based Fourier transform instruments operated at 12 sites. ACE-FTS data recorded from March 2004 to August 2007 have been used for the comparisons. These data are representative of a variety of atmospheric and chemical situations, with sounded air masses extending from the winter vortex to summer sub-tropical conditions. Typically, the ACE-FTS products are available in the 10–50 km altitude range for HCl and HF, and in the 7–20 and 7–25 km ranges for CFC-11 and -12, respectively. For both reservoirs, comparison results indicate an agreement generally better than 5–10% above 20 km altitude, when accounting for the known offset affecting HALOE measurements of HCl and HF. Larger positive differences are however found for comparisons with single profiles from FIRS-2 and SPIRALE. For CFCs, the few coincident measurements available suggest that the differences probably remain within ±20%.
Surface and boundary layer exchanges of volatile organic compounds, nitrogen oxides and ozone during the GABRIEL campaign
Authors: Ganzeveld L. , Eerdekens G. , Feig G. , Fischer H. , Harder H. , Königstedt R. , Kubistin D. , Martinez M. , Meixner F. X. , Scheeren H. A. , Sinha V. , Taraborrelli D. , Williams J. , Vilà-Guerau de Arellano J. , Lelieveld J.
Published: April 2010

Abstract. We present an evaluation of sources, sinks and turbulent transport of nitrogen oxides, ozone and volatile organic compounds (VOC) in the boundary layer over French Guyana and Suriname during the October 2005 GABRIEL campaign by simulating observations with a single-column chemistry and climate model (SCM) along a zonal transect. Simulated concentrations of O3 and NO as well as NO2 photolysis rates over the forest agree well with observations when a small soil-biogenic NO emission flux was applied. This suggests that the photochemical conditions observed during GABRIEL reflect a pristine tropical low-NOx regime. The SCM uses a compensation point approach to simulate nocturnal deposition and daytime emissions of acetone and methanol and produces daytime boundary layer mixing ratios in reasonable agreement with observations. The area average isoprene emission flux, inferred from the observed isoprene mixing ratios and boundary layer height, is about half the flux simulated with commonly applied emission algorithms. The SCM nevertheless simulates too high isoprene mixing ratios, whereas hydroxyl concentrations are strongly underestimated compared to observations, which can at least partly explain the discrepancy. Furthermore, the model substantially overestimates the isoprene oxidation products methlyl vinyl ketone (MVK) and methacrolein (MACR) partly due to a simulated nocturnal increase due to isoprene oxidation. This increase is most prominent in the residual layer whereas in the nocturnal inversion layer we simulate a decrease in MVK and MACR mixing ratios, assuming efficient removal of MVK and MACR. Entrainment of residual layer air masses, which are enhanced in MVK and MACR and other isoprene oxidation products, into the growing boundary layer poses an additional sink for OH which is thus not available for isoprene oxidation. Based on these findings, we suggest pursuing measurements of the tropical residual layer chemistry with a focus on the nocturnal depletion of isoprene and its oxidation products.