bluuebunny/crossref_metadata_2025 huggingface dataset:
Gaseous (DMS, MSA, SO2, H2SO4 and DMSO) and particulate (sulfate and methanesulfonate) sulfur species over the northeastern coast of Crete
Authors: Bardouki H. , Berresheim H. , Vrekoussis M. , Sciare J. , Kouvarakis G. , Oikonomou K. , Schneider J. , Mihalopoulos N.
Published: April 2010

Abstract. A detailed study of the levels, the temporal and diurnal variability of the main compounds involved in the biogenic sulfur cycle was carried out in Crete (Eastern Mediterranean) during the Mediterranean Intensive Oxidant Study (MINOS) field experiment in July-August 2001. Intensive measurements of gaseous dimethylsulfide (DMS), dimethylsulfoxide (DMSO), sulfur dioxide (SO2), sulfuric (H2SO4) and methanesulfonic acids (MSA) and particulate sulfate (SO42−) and methanesulfonate (MS−) have been performed during the campaign. Dimethylsulfide (DMS) levels ranged from 2.9 to 136 pmol · mol-1 (mean value of 21.7 pmol · mol−1) and showed a clear diurnal variation with daytime maximum. During nighttime DMS levels fall close or below the detection limit of 2 pmol ·mol−1. Concurrent measurements of OH and NO3 radicals during the campaign indicate that NO3 levels can explain most of the observed diurnal variation of DMS. Dimethylsulfoxide (DMSO) ranged between 0.02 and 10.1 pmol · mol−1 (mean value of 1.7 pmol · mol−1) and presents a diurnal variation similar to that of DMS. SO2 levels ranged from 220 to 2970 pmol · mol−1 (mean value of 1030 pmol · mol−1), while nss-SO42− and MS− ranged from 330 to 7100 pmol · mol−1, (mean value of 1440 pmol · mol−1) and 1.1 to 37.5 pmol · mol− (mean value of 11.5 pmol · mol−1) respectively. Of particular interest are the measurements of gaseous MSA and H2SO4. MSA ranged from below the detection limit (3×104) to 3.7×107 molecules cm−3, whereas H2SO4 ranged between 1×105 and 9.0×107 molecules cm−3. The measured H2SO4 maxima are among the highest reported in literature and can be attributed to high insolation, absence of precipitation and increased SO2 levels in the area. From the concurrent SO2, OH, and H2SO4 measurements a sticking coefficient of 0.52±0.28 was calculated for H2SO4. From the concurrent MSA, OH, and DMS measurements the yield of gaseous MSA from the OH-initiated oxidation of DMS was calculated to range between 0.1–0.4%. This low MSA yield implies that gaseous MSA levels can not account for the observed MS− levels. Heterogeneous reactions of DMSO on aerosols should be considered to explain the observed levels of MS−.
On the formation of radiation fogs under heavily polluted conditions
Authors: Kokkola H. , Romakkaniemi S. , Laaksonen A
Published: April 2010

Abstract. We have studied the effect of gaseous pollutants on fog droplet growth in heavily polluted air using a model that describes time-dependent sulfate production in the liquid phase and thermodynamical equilibrium between the droplets and the gas phase. Our research indicates that the oxidation of  SO2 to sulfate has a significant effect on fog droplet growth especially when hygroscopic trace gases, for example HNO3 andNH3 are present. The increased sulfate production by dissolution of hygroscopic gases results from increased pH (caused by absorption of ammonia) and from the increased size of the fog/smog droplets. As a result of the enhancement of the droplet growth the optical thickness of the fog will increase.
Charging of ice-vapor interfaces
Authors: Nelson J. , Baker M.
Published: April 2010

Abstract. The time resolved chemical composition of aerosol particles, formed by the oxidation of alpha-pinene has been investigated by liquid chromatography/mass spectrometry (LC-MS) using negative and positive ionisation methods (ESI(-) and APCI(+)). The experiments were performed at the EUPHORE facility in Valencia (Spain) under various experimental conditions, including dark ozone reactions, photosmog experiments with low NOx mixing ratios and reaction with OH radicals in the absence of NOx (H2O2-photolysis). Particles were sampled on PTFE filters at different stages of the reaction and extracted with methanol. The predominant products from alpha-pinene in the particulate phase are cis-pinic acid, cis-pinonic acid and hydroxy-pinonic acid isomers. Another major compound with molecular weight 172 was detected, possibly a hydroxy-carboxylic acid. These major compounds account for 50% to 80% of the identified aerosol products, depending on the time of sampling and type of experiment. In addition, more than 20 different products have been detected and structures have been tentatively assigned based on their molecular weight and responses to the different ionisation modes. The different experiments performed showed that the aerosol formation is mainly caused by the ozonolysis reaction. The highest aerosol yields were observed in the dark ozone experiments, for which also the highest ratios of mass of identified products to the formed aerosol mass were found (30% to 50%, assuming a density of 1 g cm-3).
Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes
Authors: Atkinson R.
Published: April 2010

Abstract. The available database concerning rate constants for gas-phase reactions of the hydroxyl (OH) radical with alkanes through early 2003 is presented ove the entire temperature range for which measurements have been made (~180–2000 K). Measurements made using relative rate methods are re-evaluated using recent rate data for the reference compound (generally recommendations from this review). In general, whenever more than one study has been carried out over an overlapping temperature range, recommended rate constants or temperature-dependent rate expressions are presented.
A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer
Authors: Toyota K. , Kanaya Y. , Takahashi M. , Akimoto H.
Published: April 2010

Abstract. A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry) to investigate photochemical interactions between volatile organic compounds (VOCs) and reactive halogen species in the marine boundary layer (MBL). Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit treatment of oxidative degradation of up to C3-hydrocarbons CH4, C2H6, C3H8, C2H4, C3H6, and C2H2) initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in the formation of halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO) and alkenes (especially C3H6) are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. On the other hand, the reaction between Br atoms and C2H2 is unimportant for determining the degree of bromine activation in the remote MBL. It is suggested that peroxyacetic acid formed via CH3CHO oxidation is one of the important chemical agents for triggering autocatalytic halogen release from sea-salt aerosols. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl sulfide, NOx, and O3 in the MBL.
Ground-based FTIR measurements of CO from the Jungfraujoch: characterisation and comparison with in situ surface andMOPITT data
Authors: Barret B. , De Mazière M. , Mahieu E.
Published: April 2010

Abstract. CO vertical profiles have been retrieved from solar absorption FTIR spectra recorded at the NDSC station of the Jungfraujoch (46.5° N, 8° E and 3580 m a.s.l.) for the period from January 1997 to May 2001. The characterisation of these profiles has been established by an information content analysis and an estimation of the error budgets. A partial validation of the profiles has been performed through comparisons with correlative measurements. The average volume mixing ratios (vmr) in the 3 km layer above the station have been compared with coincident surface measurements. The agreement between monthly means from both measurement techniques is very good, with a correlation coefficient of 0.87, and no significant bias observed. The FTIR total columns have also been compared to CO partial columns above 3580 m a.s.l. derived from the MOPITT (Measurement Of Pollution In The Troposphere) instrument for the period March 2000 to May 2001. Relative to the FTIR columns, the MOPITT partial columns exhibit a positive bias of 8±8% for daytime and of 4±7% for nighttime measurements.
Formation of binary ion clusters from polar vapours: Effect of the dipole-charge interaction
Authors: Nadykto A. B. , Yu F.
Published: April 2010

Abstract. Formation of binary cluster ions from polar vapours is considered. The effect of vapour polarity on the size and composition of the critical clusters is investigated theoretically and a corrected version of classical Kelvin-Thomson theory of binary ion-induced nucleation is derived. The model predictions of the derived theory are compared to the results given by classical binary homogeneous nucleation theory and ion-induced nucleation theory. The calculations are performed in wide range of the ambient conditions for a system composed of sulfuric acid and water vapour. It is shown that dipole-charge interaction significantly decreases the size of the critical clusters, especially under the atmospheric conditions when the size of critical clusters is predicted to be small.
Urban aerosol number size distributions
Authors: Hussein T. , Puustinen A. , Aalto P. P. , Mäkelä J. M. , Hämeri K. , Kulmala M.
Published: April 2010

Abstract. Aerosol number size distributions were measured continuously in Helsinki, Finland from 5 May 1997 to 28 February 2003. The daily, monthly and annual patterns were investigated. The temporal variation of the particle number concentration was seen to follow the traffic density. The highest total particle number concentrations were usually observed during workdays; especially on Fridays, and the lower concentrations occurred during weekends; especially Sundays. Seasonally, the highest total number concentrations were usually observed during winter and spring and the lowest during June and July. More than 80\\% of the particle number size distributions were tri-modal: nucleation mode (Dp < 30 nm), Aitken mode (20–100 nm) and accumulation mode (Dp > 90 nm). Less than 20% of the particle number size distributions have either two modes or consisted of more than three modes. Two different measurement sites are used; in the first place (Siltavuori, 5 May 1997–5 March 2001), the overall means of the integrated particle number concentrations were 7100 cm−3, 6320 cm−3, and 960 cm−3, respectively, for nucleation, Aitken, and accumulation modes. In the second site (Kumpula, 6 March 2001–28 February 2003) they were 5670 cm−3, 4050 cm−3, and 900 cm−3. The total number concentration in nucleation and Aitken modes were usually significantly higher during weekdays than during weekends. The variations in accumulation mode were less pronounced. The smaller concentrations in Kumpula were mainly due to building construction and also slight overall decreasing trend during these years. During the site changing a period of simultaneous measurements over two weeks were performed showing nice correlation in both sites.
Quantification of topographic venting of boundary layer air to the free troposphere
Authors: Henne S. , Furger M. , Nyeki S. , Steinbacher M. , Neininger B. , de Wekker S. F. J. , Dommen J. , Spichtinger N. , Stohl A. , Prévôt A. S. H.
Published: April 2010

Abstract. Net vertical air mass export by thermally driven f\\/lows from the atmospheric boundary layer (ABL) to the free troposphere (FT) above deep Alpine valleys was investigated. The vertical export of pollutants above mountainous terrain is presently poorly represented in global chemistry transport models (GCTMs) and needs to be quantified. Air mass budgets were calculated using aircraft observations obtained in deep Alpine valleys. The results show that on average 3 times the valley air mass is exported vertically per day under fair weather conditions. During daytime the type of valleys investigated in this study can act as an efficient "air pump" that transports pollutants upward. The slope wind system within the valley plays an important role in redistributing pollutants. Nitrogen oxide emissions in mountainous regions are efficiently injected into the FT. This enhances their ozone production efficiency and thus influences tropospheric pollution budgets. Once lifted to the FT above the Alps pollutants are transported horizontally by the synoptic flow and are subject to European pollution export. Forward trajectory studies show that under fair weather conditions two major pathways for air masses above the Alps dominate. Air masses moving north are mixed throughout the whole tropospheric column and further transported eastward towards Asia. Air masses moving south descend within the subtropical high pressure system above the Mediterranean.
Atmospheric impact of the 1783–1784 Laki eruption: Part I Chemistry modelling
Authors: Stevenson D. S. , Johnson C. E. , Highwood E. J. , Gauci V. , Collins W. J. , Derwent R. G.
Published: April 2010

Abstract. Results from the first chemistry-transport model study of the impact of the 1783–1784 Laki fissure eruption (Iceland: 64° N, 17° W) upon atmospheric composition are presented. The eruption released an estimated 122 Tg(SO2) into the troposphere and lower stratosphere. The model has a high resolution tropopause region, and detailed sulphur chemistry. The simulated SO2 plume spreads over much of the Northern Hemisphere, polewards of ~40° N. About 70% of the SO2 gas is directly deposited to the surface before it can be oxidised to sulphuric acid aerosol. The main SO2 oxidants, OH and H2O2 , are depleted by up to 40% zonally, and the lifetime of SO2 consequently in-creases. Zonally averaged tropospheric SO2 concentrations over the first three months of the eruption exceed 20 ppbv, and sulphuric acid aerosol reaches ~2 ppbv. A total aerosol yield of 51–66 Tg(H2SO4 ) is produced. The mean aerosol lifetime is only 6–9 days, and the peak aerosol loading of the atmosphere is only ~7 Tg(H2SO4.2H2O). Due to the relatively short atmospheric residence times of both the SO2 and sulphate, the aerosol loading approximately mirrors the temporal evolution of emissions associated with the eruption. The model produces a reasonable simulation of the acid deposition found in Greenland ice cores. These results appear to be relatively insensitive to the vertical profile of emissions assumed, although if more of the emissions reached higher levels (>12 km), this would give longer lifetimes and larger aerosol yields. This study suggests that most previous estimates of the global aerosol loading associated with Laki have been generally too large in magnitude, and too long-lived. Environmental effects following the Laki eruption may have been dominated by the widespread deposition of SO2 gas rather than sulphuric acid aerosol.
First retrieval of global water vapour column amounts from SCIAMACHY measurements
Authors: Noël S. , Buchwitz M. , Burrows J. P.
Published: April 2010

Abstract. Global water vapour column amounts have been derived for the first time from measurements of the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) on the European environmental satellite ENVISAT. For this purpose, two different existing retrieval algorithms have been adapted, namely the Air Mass Corrected Differential Absorption Spectroscopy (AMC-DOAS) which was originally designed for GOME and the Weighting Function Modified Differential Absorption Spectroscopy (WFM-DOAS) which was mainly designed for the retrieval of CH4, CO2 and CO from SCIAMACHY near-infrared spectra. Here, both methods have been applied to SCIAMACHY's nadir measurements in the near-visible spectral region around 700 nm. The results of these two methods agree within a scatter of ±0.5 g/cm2 with corresponding SSM/I and ECMWF water vapour data. This deviation includes contributions from the temporal and spatial variability of water vapour. In fact, the mean deviation between the SCIAMACHY and the correlative data sets is much smaller: the SCIAMACHY total water vapour columns are typically about 0.2 g/cm2 lower than the SSM/I values and less than 0.1 g/cm2 lower than corresponding ECMWF data. The SCIAMACHY water vapour results agree well with correlative data not only over ocean but also over land, thus showing the capability of SCIAMACHY to derive water vapour concentrations on the global scale.
Validation of the calibration of a laser-induced fluorescence instrument for the measurement of OH radicals in the atmosphere
Authors: Bloss W. J. , Lee J. D. , Bloss C. , Wirtz K. , Martin-Reviejo M. , Siese M. , Heard D. E. , Pilling M. J.
Published: April 2010

Abstract. An assessment of the accuracy of OH concentrations measured in a smog chamber by a calibrated laser-induced fluorescence (LIF) instrument has been made, in the course of 9 experiments performed to study the photo-oxidation of benzene, toluene, 1,3,5-trimethylbenzene, para-xylene, ortho-cresol and ethene at the European Photoreactor facility (EUPHORE). The LIF system was calibrated via the water photolysis/ozone actinometry approach. OH concentrations were inferred from the instantaneous rate of removal of each hydrocarbon species (measured by FTIR or HPLC) via the appropriate rate coefficient for their reaction with OH, and compared with those obtained from the LIF system. Good agreement between the two approaches was found for all species with the exception of 1,3,5-trimethylbenzene, for which OH concentrations inferred from hydrocarbon removal were a factor of 3 lower than those measured by the LIF system. From the remaining 8 experiments, an overall value of 1.15±0.13 (±1σ) was obtained for [OH]LIF/[OH]Hydrocarbon Decay, compared with the estimated uncertainty in the accuracy of the water photolysis/ozone actinometry OH calibration technique of 26% (1σ)
Observations of meteor-head echoes using the Jicamarca 50 MHz radar in interferometer mode
Authors: Chau J. L. , Woodman R. F.
Published: April 2010

Abstract. We present results of recent observations of meteor-head echoes obtained with the high-power large-aperture Jicamarca 50 MHz radar (11.95° S, 76.87° W) in an interferometric mode. The large power-aperture of the system allows us to record more than 3000 meteors per hour in the small volume subtended by the 1° antenna beam, albeit when the cluttering equatorial electrojet (EEJ) echoes are not present or are very weak. The interferometry arrangement allows the determination of the radiant (trajectory) and speed of each meteor. It is found that the radiant distribution of all detected meteors is concentrated in relative small angles centered around the Earth's Apex as it transients over the Jicamarca sky, i.e. around the corresponding Earth heading for the particular observational day and time, for all seasons observed so far. The dispersion around the Apex is ~18° in a direction transverse to the Ecliptic plane and only 8.5° in heliocentric longitude in the Ecliptic plane both in the Earth inertial frame of reference. No appreciable interannual variability has been observed. Moreover, no population related to the optical (larger meteors) Leonid showers of 1998–2002 is found, in agreement with other large power-aperture radar observations. A novel cross-correlation detection technique (adaptive match-filtering) is used in combination with a 13 baud Barker phase-code. The technique allows us to get good range resolution (0.75 km) without any sensitivity deterioration for the same average power, compared to the non-coded long pulse scheme used at other radars. The matching Doppler shift provides an estimation of the velocity within a pulse with the same accuracy as if a non-coded pulse of the same length had been used. The velocity distribution of the meteors is centered around 60 km s−1 corresponding to velocities slightly under the solar escape velocity (72 km s−1). Less than 8% of the velocities correspond to interstellar speeds. Higher relative velocity accuracy is obtained by cross-correlating the echoes from pulse-to-pulse, albeit with an ambiguous velocity displacement which cannot be resolved with the current observing technique. This higher relative accuracy allows the precise measurement of the deceleration of the meteors as they enter the atmosphere. In addition, an independent radial velocity is determined from the derivative of the instantaneous position. Other statistical distributions of interest are also presented.
Model study of multiphase DMS oxidation with a focus on halogens
Authors: von Glasow R. , Crutzen P. J.
Published: April 2010

Abstract. We studied the oxidation of dimethylsulfide (DMS) in the marine boundary layer (MBL) with a one-dimensional numerical model and focused on the influence of halogens. Our model runs show that there is still significant uncertainty about the end products of the DMS addition pathway, which is especially caused by uncertainty in the product yield of the reaction MSIA + OH. Under cloud-free conditions a MSA yield of only 5% in this reaction could make the addition pathway in the gas phase dominant for MSA formation whereas a yield of 0% would make the gas phase unimportant. Under cloudy conditions the uptake of  DMSO and MSIA to droplets results in a contribution of the gas phase of only about 2% to the total formation rate of MSA. The aqueous phase reaction MSIA + OH is the main source for total MSA when gas phase production of  MSA is unimportant. BrO strongly increases the importance of the addition branch in the oxidation of DMS even when present at mixing ratios smaller than 0.5 pmol mol−1. The inclusion of halogen chemistry leads to higher DMS oxidation rates and smaller DMS to SO2 conversion efficiencies. The DMS to SO2 conversion efficiency is also drastically reduced under cloudy conditions. In clouds especially during winter the aqueous phase reaction DMS + O3 contributes 4–18% to total DMS oxidation. In cloud-free model runs between 5 and 15% of the oxidized DMS reacts further to particulate sulfur, in cloudy runs this fraction is almost 100%. In general, more particulate sulfur is formed when halogen chemistry is included. A possible enrichment of HCO3 in fresh sea salt aerosol would increase pH values enough to make the reaction of S(IV)* with O3 dominant for sulfate production. It leads to a shift from MSA to nss-SO4−2 production but increases the total nss-SO4−2 only somewhat because almost all available sulfur is already oxidized to particulate sulfur in the base scenario. We discuss how realistic this is for the MBL. We found the reaction MSAaq + OH to contribute about 10\\% to the production of nss-SO4−2 in clouds. It is unimportant for cloud-free model runs. Sulfate production by HOClaq and HOBraq is important in cloud droplets even for small Br− deficits and related small gas phase halogen concentrations. We found differences in the diurnal variation of the Br− in sea salt aerosol with a peak in the morning when the loss of Br− from the sea salt is small and a peak during day when the loss is almost complete. Overall we find that the presence of halogens lead to processes that decrease the albedo of stratiform clouds in the MBL.
Classification of tropospheric ozone profiles over Johannesburg based on MOZAIC aircraft data
Authors: Diab R. D. , Raghunandan A. , Thompson A. M. , Thouret V.
Published: April 2010

Abstract. Each ozone profile is a unique response to the photochemical and dynamic processes operating in the troposphere and hence is critical to our understanding of processes and their relative contributions to the tropospheric ozone budget. Traditionally, mean profiles, together with some measure of variability, averaged by season or year at a particular location have been presented as a climatology. However, the mean profile is difficult to interpret because of the counteracting influences present in the micro-structure. On the other hand, case study analysis, whilst revealing, only applies to isolated conditions. In a search for pattern and order within ozone profiles, a classification based on a cluster analysis technique has been applied in this study. Ozone profiles are grouped according to the magnitude and altitude of ozone concentration. This technique has been tested with 56 ozone profiles at Johannesburg, South Africa, recorded by aircraft as part of the MOZAIC (Measurement of Ozone and Water Vapor aboard Airbus In-service Aircraft) program. Six distinct groups of ozone profiles have been identified and their characteristics described. The widely recognized spring maximum in tropospheric ozone is identified through the classification, but a new summertime mid-tropospheric enhancement due to the penetration of tropical air masses from continental regions in central Africa has been identified. Back trajectory modeling is used to provide evidence of the different origins of ozone enhancements in each of the classes. Continental areas over central Africa are shown to be responsible for the low to mid-tropospheric enhancement in spring and the mid-tropospheric peak in summer, whereas the winter low-tropospheric enhancement is attributed to local sources. The dominance of westerly winds through the troposphere associated with the passage of a mid-latitude cyclone gives rise to reduced ozone values.
Effects of various meteorological conditions and spatial emission resolutions on the ozone concentration & ROG/NOx limitation in the Milan area (I)
Authors: Bärtsch-Ritter N. , Keller J. , Dommen J. , Prévôt A. S. H.
Published: April 2010

Abstract. The three-dimensional photochemical model UAM-V is used to investigate the effects of various meteorological conditions and of the coarseness of emission inventories on the ozone concentration and ROG/NOx limitation of the ozone production in the Po Basin in the northern part of Italy. As a base case, the high ozone episode with up to 200 ppb on 13 May 1998 was modelled and previously thoroughly evaluated with measurements gained during a large field experiment. The performed variations in meteorology are applied to mixing height, air temperature, specific humidity and wind speed. Three coarser emission inventories are obtained by resampling from 3×3 km2 up to 54×54 km2 emission grids. The model results show that changes in meteorological input files have the largest effect on peak ozone. In the modelled ozone plume a slope of 10.1 ppb ozone/°C and in Milan of 2.8 ppb ozone/°C were found. The net ozone formation in northern Italy is more strongly temperature than humidity dependent, while the humidity is very important for the ROG/NOx limitation of the ozone production. For each of the meteorological variations (e.g. doubling the mixing height), the modelled ozone plume remains ROG limited for this case. A strong change towards NOx sensitivity in the ROG limited areas is only found if much coarser emission inventories were applied. Increasing ROG limited areas with increasing wind speed are found, because the ROG limited ozone chemistry induced by point sources is spread over a larger area. Simulations without point sources tend to increase the NOx limited areas.
Averaging kernels for DOAS total-column satellite retrievals
Authors: Eskes H. J. , Boersma K. F.
Published: April 2010

Abstract. The Differential Optical Absorption Spectroscopy (DOAS) method is used extensively to retrieve total column amounts of trace gases based on UV-visible measurements of satellite spectrometers, such as ERS-2 GOME. In practice the sensitivity of the instrument to the tracer density is strongly height dependent, especially in the troposphere. The resulting tracer profile dependence may introduce large systematic errors in the retrieved columns that are difficult to quantify without proper additional information, as provided by the averaging kernel (AK). In this paper we generalise the AK concept to total column retrievals, and derive an explicit expression for the DOAS AK. It is shown that the additional AK information corrects for the a priori dependence of the retrieval. The availability of averaging kernel information as part of the total column retrieval product is essential for the interpretation of the observations, and for applications like chemical data assimilation and detailed satellite validation studies.
Organic acids as cloud condensation nuclei: Laboratory studies of highly soluble and insoluble species
Authors: Pradeep Kumar P. , Broekhuizen K. , Abbatt J. P. D.
Published: April 2010

Abstract. The ability of sub-micron-sized organic acid particles to act as cloud condensation nuclei (CCN) has been examined at room temperature using a newly constructed continuous-flow, thermal-gradient diffusion chamber (TGDC). The organic acids studied were: oxalic, malonic, glutaric, oleic and stearic. The CCN properties of the highly soluble acids – oxalic, malonic and glutaric – match very closely Kohler theory predictions which assume full dissolution of the dry particle and a surface tension of the growing droplet equal to that of water. In particular, for supersaturations between 0.3 and 0.6, agreement between the dry particle diameter which gives 50% activation and that calculated from Kohler theory is to within 3 nm on average. In the course of the experiments, considerable instability of glutaric acid particles was observed as a function of time and there is evidence that they fragment to some degree to smaller particles. Stearic acid and oleic acid, which are both highly insoluble in water, did not activate at supersaturations of 0.6% with dry diameters up to 140 nm. Finally, to validate the performance of the TGDC, we present results for the activation of ammonium sulfate particles that demonstrate good agreement with Kohler theory if solution non-ideality is considered. Our findings support earlier studies in the literature that showed highly soluble organics to be CCN active but insoluble species to be largely inactive.
A numerical modelling study on regional mercury budget for eastern North America
Authors: Lin X. , Tao Y.
Published: April 2010

Abstract. In this study, we have integrated an up-to-date physio-chemical transformation mechanism of Hg into the framework of US EPA's CMAQ model system. In addition, the model adapted detailed calculations of the air-surface exchange for Hg to properly describe Hg re-emissions and dry deposition from and to natural surfaces. The mechanism covers Hg in three categories, elemental Hg (Hg0), reactive gaseous Hg (RGM) and particulate Hg (HgP). With interfacing to MM5 (meteorology processor) and SMOKE (emission processor), we applied the model to a 4-week period in June/July 1995 on a domain covering most of eastern North America. Results indicate that the model simulates reasonably well the levels of total gaseous Hg (TGM) and the specific Hg wet deposition measurements made by the Hg deposition network (MDN). Moreover, results from various scenario runs reveal that the Hg system behaves in a closely linear way in terms of contributions from different source categories, i.e. anthropogenic emissions, natural re-emissions and background. Analyses of the scenario results suggest that 37% of anthropogenically emitted Hg was deposited back in the model domain with 5155.2 kg of anthropogenic Hg moving out of the domain during the simulation period. Overall, the domain served as a source, which supplied a net 461.2 kg of Hg to the global background pool over the period. Our model validation and a sensitivity test further rationalized the rate constant for gaseous oxidation of Hg0 by hydroxyl radical OH used in the global scale modelling study by Bergan and Rodhe (2001). A further laboratory determination of the reaction rate constant, including its temperature dependence, stands as one of the important issues critical to improving our knowledge on the budget and cycling of Hg.
Diurnal and annual variations of meteor rates at the Arctic circle
Authors: Singer W. , Weiß J. , von Zahn U.
Published: April 2010

Abstract. Meteors are an important source for (a) the metal atoms of the upper atmosphere metal layers and (b) for condensation nuclei, the existence of which are a prerequisite for the formation of noctilucent cloud particles in the polar mesopause region. For a better understanding of these phenomena, it would be helpful to know accurately the annual and diurnal variations of meteor rates. So far, these rates have been little studied at polar latitudes. Therefore we have used the 33 MHz meteor radar of the ALOMAR observatory at 69° N to measure the meteor rates at this location for two full annual cycles. This site, being within 3° of the Arctic circle, offers in addition an interesting capability: The axis of its antenna field points (almost) towards the North ecliptic pole once each day of the year. In this particular viewing direction, the radar monitors the meteoroid influx from (almost) the entire ecliptic Northern hemisphere. We report on the observed diurnal variations (averaged over one month) of meteor rates and their significant alterations throughout the year. The ratio of maximum over minimum meteor rates throughout one diurnal cycle is in January and February about 5, from April through December 2.3±0.3. If compared with similar measurements at mid-latitudes, our expectation, that the amplitude of the diurnal variation is to decrease towards the North pole, is not really borne out. Observations with the antenna axis pointing towards the North ecliptic pole showed that the rate of deposition of meteoric dust is substantially larger during the Arctic NLC season than the annual mean deposition rate. The daylight meteor showers of the Arietids, Zeta Perseids, and Beta Taurids supposedly contribute considerably to the June maximum of meteor rates. We note, though, that with the radar antenna pointing as described above, all three meteor radiants are close to the local horizon. This radiant location should cause most of these shower meteors to occur above 100 km altitude. In our observations, the June maximum in meteor rate is produced, however, almost exclusively by meteors below 100 km altitude.
On the spectrum of vertically propagating gravity waves generated by a transient heat source
Authors: Alexander M. J. , Holton J. R.
Published: April 2010

Abstract. It is commonly believed that cumulus convection preferentially generates gravity waves with tropospheric vertical wavelengths approximately twice the depth of the convective heating. Individual cumulonimbus, however, act as short term transient heat sources (duration 10 to 30 min). Gravity waves generated by such sources have broad frequency spectra and a wide range of vertical scales. The high-frequency components tend to have vertical wavelengths much greater than twice the depth of the heating. Such waves have large vertical group velocities, and are only observed for a short duration and at short horizontal distances from the convective source. At longer times and longer distances from the source the dominant wave components have short vertical wavelengths and much slower group velocities, and thus are more likely to be observed even though their contribution to the momentum flux in the upper stratosphere and mesosphere may be less than that of the high frequency waves. These properties of convectively generated waves are illustrated by a linear numerical model for the wave response to a specified transient heat source. The wave characteristics are documented through Fourier and Wavelet analysis, and implications for observing systems are discussed.
Growth of upper tropospheric aerosols due to uptake of HNO3
Authors: Romakkaniemi S. , Kokkola H. , Petzold A. , Laaksonen A.
Published: April 2010

Abstract. The effect of nitric acid on the equilibrium size distributions of upper tropospheric aerosols is calculated as a function of relative humidity. It is shown that HNO3 concentrations above a few tenths of a ppb can cause substantial increases in haze mode particle concentrations at relative humidities at about 60% and above. The effect can be strongly magnified when letovicite particles are present in addition to sulfuric acid aerosols. This is mainly due to the lowering of the deliquescence RH of letovicite in the presence of gaseous nitric acid at low temperatures. We have also compared equilibrium calculations of the HNO3 effect with observations of increased haze mode concentrations at relative humidities above 50% (Petzold et al., 2000). Nitric acid mixing ratios on the order of 0.5–2 ppb may explain the observed increase of haze mode particles at least partially.
Meteor velocity determination with plasma physics
Authors: Dyrud L. P. , Denney K. , Close S. , Oppenheim M. , Ray L. , Chau J.
Published: April 2010

Abstract. Understanding the global meteor flux at Earth requires the measurement of meteor velocities. While several radar methods exist for measuring meteor velocity, they may be biased by plasma reflection mechanisms. This paper presents a new method for deriving meteoroid velocity from the altitudinal extent of non-specular trails. This method employs our recent discoveries on meteor trail plasma instability. Dyrud et al. (2002) demonstrated that meteor trails are unstable over a limited altitude range, and that the precise altitudes of instability are dependent on the meteoroid velocity that generated the trail. Since meteor trail instability results in field aligned irregularities (FAI) that allow for radar reflection, non-specular trail observations may be used to derive velocity. We use ALTAIR radar data of combined head echos and non-specular trails to test non-specular trail derived velocity against head echo velocities. Meteor velocities derived from non-specular trail altitudinal width match to within 5 km/s when compared with head echo range rates from the same meteor. We apply this technique to Piura radar observations of hundreds of non-specular trails to produce histograms of occurrence of meteor velocity based solely on this non-specular trails width criterion. The results from this study show that the most probable velocity of meteors seen by the Piura radar is near 50 km/s which is comparable with modern head echo studies.
Partially oxidised organic components in urban aerosol using GCXGC-TOF/MS
Authors: Hamilton J. , Webb P. , Lewis A. , Hopkins J. , Smith S. , Davy P.
Published: April 2010

Abstract. Partially oxidised organic compounds associated with PM2.5 aerosol collected in London, England, have been analysed using direct thermal desorption coupled to comprehensive gas chromatography-time of flight mass spectrometry (GCXGC-OF/MS). Over 10 000 individual organic components were isolated from around 10 μg of aerosol material in a single procedure and with no sample pre-treatment. Chemical functionalities observed using this analytical technique ranged from alkanes to poly-oxygenated species. The chemical band structures commonly used in GCXGC for group type identifications overlap for this sample type, and have required mass spectrometry as an additional level of instrument dimensionality. An investigation of oxygenated volatile organic compounds (o-VOC) contained within urban aerosol has been performed and in a typical sample around 130 o-VOCs were identified based on retention behaviour and spectral match. In excess of 100 other oxygenated species were also observed but lack of mass spectral library or pure components prevents positive identification. Many of the carbonyl species observed could be mechanistically linked to gas phase aromatic hydrocarbon oxidation and there is good agreement in terms of speciation between the urban samples analysed here and those degradation products observed in smog chamber experiments of aromatic oxidation. The presence of partially oxidised species such as linear chain aldehydes and ketones and cyclic products such as furanones suggests that species generated relatively early in the oxidative process may undergo gas to particle partitioning despite their relatively high volatility.
Gas-particle interactions above a Dutch heathland: II. Concentrations and surface exchange fluxes of atmospheric particles
Authors: Nemitz E. , Sutton M. A. , Wyers G. P. , Otjes R. P. , Mennen M. G. , van Putten E. M. , Gallagher M. W.
Published: April 2010

Abstract. Size-dependent particle number fluxes measured by eddy-covariance (EC) and continuous fluxes of ammonium (NH4+) measured with the aerodynamic gradient method (AGM) are reported for a Dutch heathland. Daytime deposition velocities (Vd) by EC with peak values of 5 to 10 mm s−1 increased with particle diameter (dp) over the range 0.1–0.5 μm, and are faster than predicted by current models. With a mean Vd of 2.0 mm s−1 (daytime: 2.7; night-time 0.8 mm s−1) NH4+ fluxes by AGM are overall in agreement with former measurements and NH4+-N dry deposition amounts to 20% of the dry input of NH3-N over the measurement period. These surface exchange fluxes are analyzed together with simultaneous gas-phase flux measurements for indications of gas-particle interactions. On warm afternoons the apparent fluxes of acids and aerosol above the heathland showed several coinciding anomalies, all of which are consistent with NH4+ evaporation during deposition: (i) canopy resistances for HNO3 and HCl of up to 100 s m−1, (ii) simultaneous particle emission of small particles (Dp<0.18 μm) and deposition of larger particles (Dp>0.18 μm), (iii) NH4+ deposition faster than derived from size-distributions and size-segregated EC particle fluxes. These observations coincide with the observations of (i) surface concentration products of NH3 and HNO3 well below the thermodynamic equilibrium value and (ii) Damköhler numbers that indicate chemical conversion to be sufficiently fast to modify exchange fluxes. The measurements imply a removal rate of volatile NH4+ of 3–30×10−6s−1 averaged over the 1 km boundary-layer, while NH3 deposition is underestimated by typically 20 ng m−2 s−1 (28%) and flux reversal may occur.
Circumpolar transport and air-surface exchange of atmospheric mercury at Ny-Ålesund (79° N), Svalbard, spring 2002
Authors: Sommar J. , Wängberg I. , Berg T. , Gårdfeldt K. , Munthe J. , Richter A. , Urba A. , Wittrock F. , Schroeder W. H.
Published: April 2010

Abstract. Mercury in different environmental compartments has been measured at Ny-Ålesund (78°54′ N, 11°53′ E) during an intensive campaign, 17 April to 14 May 2002. Time-resolved speciated determination of mercury in the atmosphere and snow was conducted at the Norwegian research station at the Zeppelin mountain, 474 m above the sea level, and at the Italian research facility Dirigibile Italia, 12 m above the sea level. Total Gaseous Mercury (TGM) was present in the range <0.1 to 2.2 ng m−3 during the campaign. Three mercury depletion events, identified as periods with decreased TGM concentrations, were observed. At the lower altitude, TGM concentrations following such events were found to exhibit both higher magnitude and larger variability in comparison to results from the Zeppelin station. Oxidised mercury species in air and fall-out with snow as well as mercury attached to particles were also measured and their concentrations were found to be anti-correlated with TGM in air. The strongest modulation was observed for total mercury concentration (Hg-tot) in snow (range 1.5–76.5 ng L−1). Solid evidence for photo-stimulated emissions of Hg0(g) from the snow pack in conjunction to depletion events were obtained from gradient measurements as well as from flux chamber measurements. Steep diurnal concentration variations of Hg0(aq) in surface seawater were also found to concur with changing solar radiation. The concentration of Hg0(aq) in seawater was found to be in the range 12.2–70.4 pg L−1, which corresponds to supersaturation. Hence, the seawater surface constituted a source emitting elemental mercury. The concentrations of the transient mercury forms RGM (Reactive Gaseous Mercury) and PM (Particulate Mercury) respectively and BrO column densities detected using a zenith and off-axis sky viewing DOAS instrument were very low except for a few individual samples during the major depletion event. An evaluation of trajectories for selected events and comparisons with BrO vertical column densities obtained by the GOME (Global Ozone Monitoring Experiment) instrument aboard the earth remote sensing satellite ESR-2 indicates that the air masses exhibiting low Hg0 concentrations originated from areas with high BrO densities. It was concluded that the observed depletion events at Ny-Ålesund were a results of transport from areas with high photochemical activity around the polar region.
Heterogeneous freezing of single sulphuric acid solution droplets: laboratory experiments utilising an acoustic levitator
Authors: Ettner M. , Mitra S. K. , Borrmann S.
Published: April 2010

Abstract. The heterogeneous freezing temperatures of single binary sulphuric acid solution droplets were measured in dependency of acid concentration down to temperatures as low as −70°C. In order to avoid influence of supporting substrates on the freezing characteristics, the droplets were suspended by means of an acoustic levitator. The droplets contained immersed particles of graphite, kaolin or montmorillonite in order to study the influence of the presence of such contamination on the freezing temperature. The radii of the suspended droplets spanned the range between 0,4 and 1,1 mm and the concentration of the sulphuric acid solution varied between 5 and 25 weight percent. The presence of the particles in the solution raises the freezing temperature with respect to homogeneous freezing of these solution droplets. The pure solution droplets can be supercooled up to 40° below the ice-acid solution thermodynamic equilibrium curve. Depending on the concentration of sulphuric acid and the nature of the impurity the polluted droplets froze between −11°C and −35°C. The experimental set-up, combining a deep freezer with a movable ultrasonic levitator and suitable optics, proved to be a useful approach for such investigations on individual droplets.
Quantification of the impact in mid-latitudes of chemical ozone depletion in the 1999/2000 Arctic polar vortex prior to the vortex breakup
Authors: Koch G. , Wernli H. , Buss S. , Staehelin J. , Peter T. , Liniger M. A. , Meilinger S.
Published: April 2010

Abstract. For the winter 1999/2000 transport of air masses out of the vortex to mid-latitudes and ozone destruction inside and outside the northern polar vortex is studied to quantify the impact of earlier winter (before March) polar ozone destruction on mid-latitude ozone. Nearly 112 000 trajectories are started on 1 December 1999 on 6 different potential temperature levels between 500–600 K and for a subset of these trajectories photo-chemical box-model calculations are performed. We linked a decline of −0.9% of mid-latitude ozone in this layer occurring in January and February 2000 to ozone destruction inside the vortex and successive transport of these air masses to mid-latitudes. Further, the impact of denitrification, PSC-occurrence and anthropogenic chlorine loading on future stratospheric ozone is determined by applying various scenarios. Lower stratospheric temperatures and denitrification were found to play the most important role in the future evolution of polar ozone depletion.