bluuebunny/crossref_metadata_2025 huggingface dataset:
Distribution and sources of bioaccumulative air pollutants at Mezquital Valley, Mexico, as reflected by the atmospheric plant Tillandsia recurvata L.
Authors: Zambrano García A. , Medina Coyotzin C. , Rojas Amaro A. , López Veneroni D. , Chang Martínez L. , Sosa Iglesias G.
Published: April 2010

Abstract. Mezquital Valley (MV), a Mexican wastewater-based agricultural and industrial region, is a "hot spot" of regulated air pollutants emissions, but the concurrent unregulated ones, like hazardous metals and polycyclic aromatic hydrocarbons (PAH), remain undocumented. A biomonitoring survey with the epiphytic Tillandsia recurvata was conducted there to detect spatial patterns and potential sources of 20 airborne elements and 15 PAH. The natural δ13C and δ15N ratios of this plant helped in source identification. The regional mean concentration of most elements was two (Cr) to over 40 times (Ni, Pb, V) higher than reported for Tillandsia in other countries. Eleven elements, pyrene and chrysene had 18–214% higher mean concentration at the industrial south than at the agricultural north of MV. The total quantified PAH (mean, 572 ng g−1; range, 143–2568) were composed by medium (65%, phenanthrene to chrysene), low (28%, naphthalene to fluorene) and high molecular weight compounds (7%, Benzo(b)fluoranthene to indeno(1,2,3-cd)pyrene). The δ13C (mean, −14.6‰; range, −15.7‰ to −13.7‰) was consistently lower than −15‰ near the major petroleum combustion sources. The δ15N (mean, −3.0‰; range, −9.9‰ to 3.3‰) varied from positive at agriculture/industrial areas to negative at rural sites. Factor analysis provided a five-factor solution for 74% of the data variance: 1) crustal rocks, 39.5% (Al, Ba, Cu, Fe, Sr, Ti); 2) soils, 11.3%, contrasting contributions from natural (Mg, Mn, Zn) and saline agriculture soils (Na); 3) cement production and fossil fuel combustion, 9.8% (Ca, Ni, V, chrysene, pyrene); 4) probable agricultural biomass burning, 8.1% (K and benzo(g,h,i)perylene), and 5) agriculture with wastewater, 5.2% (δ15N and P). These results indicated high deposition of bioaccumulative air pollutants at MV, especially at the industrial area. Since T. recurvata reflected the regional differences in exposition, it is recommended as a biomonitor for comparisons within and among countries where it is distributed: southern USA to Argentina.
Limb scatter ozone retrieval from 10 to 60 km using a multiplicative algebraic reconstruction technique
Authors: Degenstein D. A. , Bourassa A. E. , Roth C. Z. , Llewellyn E. J.
Published: April 2010

Abstract. The OSIRIS instrument onboard the Odin spacecraft routinely measures vertical profiles of spectrally dispersed, limb scattered sunlight from the upper troposphere into the lower mesosphere. These measurements are used to retrieve the ozone number density vertical profile using the SaskMART Multiplicative Algebraic Reconstruction Technique, which is a one dimensional modification of an existing two-dimensional tomographic retrieval algorithm. The retrieved profile extends from the cloud top to 60 km. In the absence of clouds the retrieval extends down to 10 km. This technique allows for the consistent merging of the absorption information from radiance measurements at wavelengths in the Chappuis and the Hartley-Huggins bands at each iteration of the inversion. The effectiveness of the retrieval is demonstrated using a set of coincident SAGE II occultation measurements that show a mean bias of less than 2% from 18 to 53 km.
The impact of MM5 and WRF meteorology over complex terrain on CHIMERE model calculations
Authors: de Meij A. , Gzella A. , Cuvelier C. , Thunis P. , Bessagnet B. , Vinuesa J. F. , Menut L. , Kelder H. M.
Published: April 2010

Abstract. The objective of this study is to evaluate the impact of meteorological input data on calculated gas and aerosol concentrations. We use two different meteorological models (MM5 and WRF) together with the chemistry transport model CHIMERE. We focus on the Po valley area (Italy) for January and June 2005. Firstly we evaluate the meteorological parameters with observations. The analysis shows that the performance of both models in calculating surface parameters is similar, however differences are still observed. Secondly, we analyze the impact of using MM5 and WRF on calculated PM10 and O3 concentrations. In general CHIMERE/MM5 and CHIMERE/WRF underestimate the PMv concentrations for January. The difference in PM10 concentrations for January between CHIMERE/MM5 and CHIMERE/WRF is around a factor 1.6 (PM10 higher for CHIMERE/MM5). This difference and the larger underestimation in PM10 concentrations by CHIMERE/WRF are related to the differences in heat fluxes and the resulting PBL heights calculated by WRF. In general the PBL height by WRF meteorology is a factor 2.8 higher at noon in January than calculated by MM5. This study showed that the difference in microphysics scheme has an impact on the profile of cloud liquid water (CLW) calculated by the meteorological driver and therefore on the production of SO4 aerosol. A sensitivity analysis shows that changing the Noah Land Surface Model (LSM) in our WRF pre-processing for the 5-layer soil temperature model, calculated monthly mean PMv concentrations increase by 30%, due to the change in the heat fluxes and the resulting PBL heights. For June, PM10 calculated concentrations by CHIMERE/MM5 and CHIMERE/WRF are similar and agree with the observations. Calculated O3 values for June are in general overestimated by a factor 1.3 by CHIMERE/MM5 and CHIMERE/WRF. High temporal correlations are found between modeled and observed O3 concentrations.
Measurements of OH and HO2concentrations during the MCMA-2006 field campaign – Part 2: Model comparison and radical budget
Authors: Dusanter S. , Vimal D. , Stevens P. S. , Volkamer R. , Molina L. T. , Baker A. , Meinardi S. , Blake D. , Sheehy P. , Merten A. , Zhang R. , Zheng J. , Fortner E. C. , Junkermann W. , Dubey M. , Rahn T. , Eichinger B. , Lewandowski P. , Prueger J. , Holder H.
Published: April 2010

Abstract. Measurements of hydroxyl (OH) and hydroperoxy (HO2) radicals were made during the Mexico City Metropolitan Area (MCMA) field campaign as part of the MILAGRO (Megacity Initiative: Local and Global Research Observations) project during March 2006. These measurements provide a unique opportunity to test current models of atmospheric ROx (OH + HO2 + RO2) photochemistry under polluted conditions. A zero-dimensional box model based on the Regional Atmospheric Chemical Mechanism (RACM) was constrained by 10-min averages of 24 J-values and the concentrations of 97 chemical species. Several issues related to the ROx chemistry under polluted conditions are highlighted in this study: (i) Measured concentrations of both OH and HO2 were underpredicted during morning hours on a median campaign basis, suggesting a significant source of radicals is missing from current atmospheric models under polluted conditions, consistent with previous urban field campaigns. (ii) The model-predicted HO2/OH ratios underestimate the measurements for NO mixing ratios higher than 5 ppb, also consistent with previous urban field campaigns. This suggests that under high NOx conditions, the HO2 to OH propagation rate may be overestimated by the model or a process converting OH into HO2 may be missing from the chemical mechanism. On a daily basis (08:40 a.m.–06:40 p.m.), an analysis of the radical budget indicates that HONO photolysis, HCHO photolysis, O3-alkene reactions and dicarbonyls photolysis are the main radical sources. O3 photolysis contributes to less than 6% of the total radical production.
Influence of particle size on the ice nucleating ability of mineral dusts
Authors: Welti A. , Lüönd F. , Stetzer O. , Lohmann U.
Published: April 2010

Abstract. The recently developed Zurich Ice Nucleation Chamber (ZINC) was used to explore ice nucleation of size-selected mineral dust particles at temperatures between −20°C and −55°C. Four different mineral dust species have been tested: montmorillonite, kaolinite, illite and Arizona test dust (ATD). The selected particle diameters are 100 nm, 200 nm, 400 nm and 800 nm. Relative humidities with respect to ice (RHi) required to activate 1% of the dust particles as ice nuclei (IN) are reported as a function of temperature. An explicit size dependence of the ice formation efficiency has been observed for all dust types. 800 nm particles required the lowest RHi to activate. Deposition nucleation below water saturation was found only below −30°C or −35°C dependent on particle size. Minimum RHi for 1% activation were 105% for illite, kaolinite and montmorillonite at −40°C, respectively 110% for ATD at −45°C. In addition, a possible parameterisation for the measured activation spectra is proposed, which could be used in modeling studies.
A comparison study of regional atmospheric simulations with an elastic backscattering Lidar and sunphotometry in an urban area
Authors: Landulfo E. , Freitas S. R. , Longo K. M. , Uehara S. T. , Sawamura P.
Published: April 2010

Abstract. We describe a comparison study of Aerosol Optical Thickness (AOT) from numerical simulations using a regional atmospheric model with an elastic backscattering lidar operating at 532 nm and a sunphotometer belonging to the AERONET network at São Paulo (23° S 46° W) city, Brazil, a very populated urban area. The atmospheric model includes an aerosol emission, transport and deposition module coupled to a radiative transfer parameterization, which takes the interaction between aerosol particles and short and long wave radiation into account. A period of one week was taken as case study during the dry season (late August) when intense biomass burning activities occur at remote areas in South America, and meteorological conditions disfavor the pollution dispersion in the city of São Paulo. The situation presented here showed how smoke from biomass burning in remote areas is transported to the south-east part of Brazil and affects the optical atmospheric conditions in São Paulo. The numerical simulations are corroborated by in situ measurements of AOT obtained by lidar and sun photometry.
What can we learn about ship emission inventories from measurements of air pollutants over the Mediterranean Sea?
Authors: Marmer E. , Dentener F. , Aardenne J. v. , Cavalli F. , Vignati E. , Velchev K. , Hjorth J. , Boersma F. , Vinken G. , Mihalopoulos N. , Raes F.
Published: April 2010

Abstract. Ship emission estimates diverge widely for all chemical compounds for several reasons: use of different methodologies (bottom-up or top-down), activity data and emission factors can easily result in a difference ranging from a factor of 1.5 to even an order of magnitude. Combining three sets of observational data – ozone and black carbon measurements sampled at three coastal sites and on board of a Mediterranean cruise ship, as well as satellite observations of atmospheric NO2 column concentration over the same area – we assess the accuracy of the three most commonly used ship emission inventories, EDGAR FT (Olivier et al., 2005), emissions described by Eyring et al. (2005) and emissions reported by EMEP (Vestreng et al., 2007). Our tool is a global atmospheric chemistry transport model which simulates the chemical state of the Mediterranean atmosphere applying different ship emission inventories. The simulated contributions of ships to air pollutant levels in the Mediterranean atmosphere are significant but strongly depend on the inventory applied. Close to the major shipping routes relative contributions vary from 10 to 50% for black carbon and from 2 to 12% for ozone in the surface layer, as well as from 5 to 20% for nitrogen dioxide atmospheric column burden. The relative contributions are still significant over the North African coast, but less so over the South European coast because densely populated regions with significant human activity contribute relatively more to air pollution than ships, even if these regions attract a lot of ship traffic. The observations poorly constrain the ship emission inventories in the Eastern Mediterranean where the influence of uncertain land based emissions, the model transport and wet deposition are at least as important as the signal from ships. In the Western Mediterranean, the regional EMEP emission inventory gives the best match with most measurements, followed by Eyring for NO2 and ozone and by EDGAR for black carbon. Given the uncertainty of the measurements and the model, each of the three emission inventories could actually be right, implying that large uncertainties in ship emissions need to be considered for future scenario analysis.
Hygroscopic growth of urban aerosol particles in Beijing (China) during wintertime: a comparison of three experimental methods
Authors: Meier J. , Wehner B. , Massling A. , Birmili W. , Nowak A. , Gnauk T. , Brüggemann E. , Herrmann H. , Min H. , Wiedensohler A.
Published: April 2010

Abstract. The hygroscopic properties of atmospheric aerosols are highly relevant for the quantification of radiative effects in the atmosphere, but also of interest for the assessment of particle health effects upon inhalation. This article reports measurements of aerosol particle hygroscopicity in the highly polluted urban atmosphere of Beijing, China in January 2005. The meteorological conditions corresponded to a relatively cold and dry atmosphere. Three different methods were used: 1) A combination of Humidifying Differential Mobility Particle Sizer (H-DMPS) and Twin Differential Mobility Particle Sizer (TDMPS) measurements, 2) A Hygroscopic Tandem Differential Mobility Analyzer (H-TDMA), and 3) A simplistic solubility model fed by chemical particle composition determined from Micro Orifice Uniform Deposit Impactor (MOUDI) samples. From the H-DMPS and TDMPS particle number size distributions, a size-resolved descriptive hygroscopic growth factor (DHGF) was determined for the relative humidities (RH) 55%, 77% and 90%, and particle diameters between 30 and 400 nm. In Beijing, the highest DHGFs were observed for accumulation mode particles, 1.40 (±0.03) at 90% RH. DHGF decreased significantly with particle size, reaching 1.04 (±0.15) at 30 nm. H-TDMA data also suggest a decrease in growth factor towards the biggest particles investigated (350 nm), associated with an increasing fraction of nearly hydrophobic particles. The agreement between the H-DMPS/TDMPS and H-TDMA methods was satisfactory in the accumulation mode size range (100–400 nm). In the Aitken mode range (<100 nm), the H-DMPS/TDMPS method yielded growth factors lower by up to 0.1 at 90% RH. The application of the solubility model based on measured chemical composition clearly reproduced the size-dependent trend in hygroscopic particle growth observed by the other methods. In the case of aerosol dominated by inorganic ions, the composition-derived growth factors tended to agree (± 0.05) or underestimate (up to 0.1) the values measured by the other two methods. In the case of aerosol dominated by organics, the reverse was true, with an overestimation of up to 0.2. The results shed light on the experimental and methodological uncertainties that are still connected with the determination of hygroscopic growth factors.
Nitric acid in the stratosphere based on Odin observations from 2001 to 2009 – Part 1: A global climatology
Authors: Urban J. , Pommier M. , Murtagh D. P. , Santee M. L. , Orsolini Y. J.
Published: April 2010

Abstract. The Sub-Millimetre Radiometer (SMR) on board the Odin satellite, launched in February 2001, observes thermal emissions of stratospheric nitric acid (HNO3) originating from the Earth limb in a band centred at 544.6 GHz. Height-resolved measurements of the global distribution of nitric acid in the stratosphere were performed approximately on two observation days per week. An HNO3 climatology based on more than 7 years of observations from August 2001 to April 2009 covering the vertical range between typically ~19 and 45 km (~1.5–60 hPa or ~500–1800 K in terms of potential temperature) was created. The study highlights the spatial and seasonal variation of nitric acid in the stratosphere, characterised by a pronounced seasonal cycle at middle and high latitudes with maxima during late fall and minima during spring, strong denitrification in the lower stratosphere of the Antarctic polar vortex during winter (the irreversible removal of NOy by the sedimentation of cloud particles containing HNO3), as well as large quantities of HNO3 formed every winter at high-latitudes in the middle and upper stratosphere. A strong inter-annual variability is observed in particular at high latitudes. A comparison with a stratospheric HNO3 climatology, based on over 7 years of UARS/MLS (Upper Atmosphere Research Satellite/Microwave Limb Sounder) measurements from the 1990s, shows good consistency and agreement of the main morphological features in the potential temperature range ~465 to ~960 K, if the different characteristics of the data sets such as the better altitude resolution of Odin/SMR as well as the slightly different altitude ranges are considered. Odin/SMR reaches higher up and UARS/MLS lower down in the stratosphere. An overview from 1991 to 2009 of stratospheric nitric acid is provided (with a short gap between 1998 and 2001), if the global measurements of both experiments are taken together.
Regional modelling of tracer transport by tropical convection – Part 1: Sensitivity to convection parameterization
Authors: Arteta J. , Marécal V. , Rivière E. D.
Published: April 2010

Abstract. The general objective of this series of papers is to evaluate long duration limited area simulations with idealised tracers as a tool to assess tracer transport in chemistry-transport models (CTMs). In this first paper, we analyse the results of six simulations using different convection closures and parameterizations. The simulations are using the Grell and Dévényi (2002) mass-flux framework for the convection parameterization with different closures (Grell = GR, Arakawa-Shubert = AS, Kain-Fritch = KF, Low omega = LO, Moisture convergence = MC) and an ensemble parameterization (EN) based on the other five closures. The simulations are run for one month during the SCOUT-O3 field campaign lead from Darwin (Australia). They have a 60 km horizontal resolution and a fine vertical resolution in the upper troposphere/lower stratosphere. Meteorological results are compared with satellite products, radiosoundings and SCOUT-O3 aircraft campaign data. They show that the model is generally in good agreement with the measurements with less variability in the model. Except for the precipitation field, the differences between the six simulations are small on average with respect to the differences with the meteorological observations. The comparison with TRMM rainrates shows that the six parameterizations or closures have similar behaviour concerning convection triggering times and locations. However, the 6 simulations provide two different behaviours for rainfall values, with the EN, AS and KF parameterizations (Group 1) modelling better rain fields than LO, MC and GR (Group 2). The vertical distribution of tropospheric tracers is very different for the two groups showing significantly more transport into the TTL for Group 1 related to the larger average values of the upward velocities. Nevertheless the low values for the Group 1 fluxes at and above the cold point level indicate that the model does not simulate significant overshooting. For stratospheric tracers, the differences between the two groups are small indicating that the downward transport from the stratosphere is more related to the turbulent mixing parameterization than to the convection parameterization.
Impact of dust aerosols on the radiative budget, surface heat fluxes, heating rate profiles and convective activity over West Africa during March 2006
Authors: Mallet M. , Tulet P. , Serça D. , Solmon F. , Dubovik O. , Pelon J. , Pont V. , Thouron O.
Published: April 2010

Abstract. The present work analyses the effect of dust aerosols on the surface and top of atmosphere radiative budget, surface temperature, sensible heat fluxes, atmospheric heating rate and convective activity over West Africa. The study is focused on the regional impact of a major dust event over the period of 7–14 March 2006 through numerical simulations performed with the mesoscale, nonhydrostatic atmospheric model MesoNH. Due to its importance on radiative budgets, a specific attention has been paid to the representation of dust single scattering albedo (SSA) in MesoNH by using inversions of the AErosol RObotic NETwork (AERONET). The radiative impacts are estimated using two parallel simulations, one including radiative effects of dust and the other without them. The simulations of dust aerosol impacts on the radiative budget indicate remarkable instantaneous (at midday) decrease of surface shortwave (SW) radiations over land, with regional (9°–17° N, 10° W–20° E) mean of −137 W/m2 during the 9 to 12 March period. The surface dimming resulting from the presence of dust is shown to cause important reduction of both surface temperature (up to 4°C) and sensible heat fluxes (up to 100 W/m2), which is consistent with experimental observations. At the top of the atmosphere, the SW cooling (regional mean of −12.0 W/m2) induced by mineral dust is shown to dominate the total net (shortwave + longwave) effect. The maximum SW heating occurs within the dusty layer with values comprised between 4 and 7° K by day and LW effect results in a cooling of −0.10/−0.20° K by day. Finally, the simulations suggest the decrease of the convective available potential energy (CAPE) over the region in the presence of mineral dust.
Constraints on inorganic gaseous iodine in the tropical upper troposphere and stratosphere inferred from balloon-borne solar occultation observations
Authors: Butz A. , Bösch H. , Camy-Peyret C. , Chipperfield M. P. , Dorf M. , Kreycy S. , Kritten L. , Prados-Román C. , Schwärzle J. , Pfeilsticker K.
Published: April 2010

Abstract. We report upper limits of IO and OIO in the tropical upper troposphere and stratosphere inferred from solar occultation spectra recorded by the LPMA/DOAS (Limb Profile Monitor of the Atmosphere/Differential Optical Absorption Spectroscopy) payload during two stratospheric balloon flights from a station in Northern Brazil (5.1° S, 42.9° W). In the tropical upper troposphere and lower stratosphere, upper limits for both, IO and OIO, are below 0.1 ppt. Photochemical modelling is used to estimate the compatible upper limits for the total gaseous inorganic iodine burden (Iy) amounting to 0.09 to 0.16 (+0.10/−0.04) ppt in the tropical lower stratosphere (21.0 km to 16.5 km) and 0.17 to 0.35 (+0.20/−0.08) ppt in the tropical upper troposphere (16.5 km to 13.5 km). In the middle stratosphere, upper limits increase with altitude as sampling sensitivity decreases. Our findings imply that the amount of gaseous iodine transported into the stratosphere through the tropical tropopause layer is small. Thus, iodine-mediated ozone loss plays a minor role for contemporary stratospheric photochemistry but might become significant in the future if source gas emissions or injection efficiency into the upper atmosphere are enhanced. However, photochemical modelling uncertainties are large and iodine might be transported into the stratosphere in particulate form.
Influence of line mixing on the retrievals of atmospheric CO2 from spectra in the 1.6 and 2.1 μm regions
Authors: Hartmann J.-M. , Tran H. , Toon G. C.
Published: April 2010

Abstract. We present the first study of the influence of line mixing among CO2 lines on the remote sensing retrieval of atmospheric carbon dioxide. This is done in the bands near 1.6 and 2.1 μm which will be used by the Greenhouse Gases Observatory Satellite (GOSAT) instrument and eventual successors of the Orbiting Carbon Observatory (OCO). A purely theoretical analysis is first made, based on simulations of atmospheric spectra. It shows that line mixing cannot be neglected since disregarding this process induces significant errors in the calculated absorption coefficients, leading to systematic structures in the spectral fit residuals and airmass-dependent biases in the retrieved CO2 amounts. These theoretical predictions are then confirmed by using atmospheric solar-absorption spectra measured by a ground-based Fourier transform spectrometer. It is first shown that including line mixing in the forward model used for the inversion leads to a very significant reduction of the residuals in the 2.1 μm region. Secondly, the inclusion of line mixing reduces the dependence of the retrieved CO2 on the airmass and greatly improves the consistency between values obtained independently from spectra in the 1.6 and 2.1 μm bands. These results open promising prospects for various ground-based and space-borne experiments monitoring the carbon dioxide atmospheric amounts.
Eddy covariance flux measurements of pollutant gases in urban Mexico City
Authors: Velasco E. , Pressley S. , Grivicke R. , Allwine E. , Coons T. , Foster W. , Jobson B. T. , Westberg H. , Ramos R. , Hernández F. , Molina L. T. , Lamb B.
Published: April 2010

Abstract. Eddy covariance (EC) flux measurements of the atmosphere/surface exchange of gases over an urban area are a direct way to improve and evaluate emissions inventories, and, in turn, to better understand urban atmospheric chemistry and the role that cities play in regional and global chemical cycles. As part of the MCMA-2003 study, we demonstrated the feasibility of using eddy covariance techniques to measure fluxes of selected volatile organic compounds (VOCs) and CO2 from a residential district of Mexico City (Velasco et al., 2005a, b). During the MILAGRO/MCMA-2006 field campaign, a second flux measurement study was conducted in a different district of Mexico City to corroborate the 2003 flux measurements, to expand the number of species measured, and to obtain additional data for evaluation of the local emissions inventory. Fluxes of CO2 and olefins were measured by the conventional EC technique using an open path CO2 sensor and a Fast Isoprene Sensor calibrated with a propylene standard. In addition, fluxes of toluene, benzene, methanol and C2-benzenes were measured using a virtual disjunct EC method with a Proton Transfer Reaction Mass Spectrometer. The flux measurements were analyzed in terms of diurnal patterns and vehicular activity and were compared with the most recent gridded local emissions inventory. In both studies, the results showed that the urban surface of Mexico City is a net source of CO2 and VOCs with significant contributions from vehicular traffic. Evaporative emissions from commercial and other anthropogenic activities were significant sources of toluene and methanol. The results show that the emissions inventory is in reasonable agreement with measured olefin and CO2 fluxes, while C2-benzenes and toluene emissions from evaporative sources are overestimated in the inventory. It appears that methanol emissions from mobile sources occur, but are not reported in the mobile emissions inventory.
Concurrent observations of air pollutants at two sites in the Pearl River Delta and the implication of regional transport
Authors: Guo H. , Jiang F. , Cheng H. R. , Simpson I. J. , Wang X. M. , Ding A. J. , Wang T. J. , Saunders S. M. , Wang T. , Lam S. H. M. , Blake D. R. , Zhang Y. L. , Xie M.
Published: April 2010

Abstract. An intensive field measurement study was conducted simultaneously at a site within the inland Pearl River Delta (PRD) region (WQS) and a site in Hong Kong (TC) between 22 October and 1 December 2007. Ambient air pollutants measured included O3, NOx, CO, SO2, NMHCs, and carbonyls. The purpose is to improve our understanding of the interplay among local and regional air pollutants in the Hong Kong area, and the influence of regional transport on local air pollutants. The results indicate that the mean levels of air pollutants at the WQS site were much higher than those at the TC site, except NOx. Thirteen O3 episode days (daily O3 peak in excess of 122 ppbv) were monitored at WQS during the study period, while only 2 days were recorded at TC. Diurnal variations of O3 showed higher nighttime levels of O3 at TC than at WQS as well as more photochemical activity at WQS than TC. Remarkable differences in diurnal variations were also found between high and low O3 pollution days at each site, implying that Hong Kong is more acutely VOC-limited than the inland PRD region. Ratio analyses for trace gases and VOCs and back trajectory calculation revealed that the air masses arriving at WQS were more aged due to regional influence, whereas the air masses at TC were mainly affected by local emissions and/or regional transport. In addition, the influence of regional transport from Eastern China on the primary pollutants of Hong Kong was noticeable, whereas the air masses from the inland PRD region (e.g. Dongguan and Huizhou) had significant influence on the air pollutants at WQS, and the anthropogenic emissions in Eastern PRD (e.g. Shenzhen) played an important role on the photochemical ozone pollution in Western Hong Kong. These results confirm that regional and sub-regional transport of air pollution has a complex and significant impact on local air pollutants in this region.
Atmospheric hydrogen variations and traffic emissions at an urban site in Finland
Authors: Aalto T. , Lallo M. , Hatakka J. , Laurila T.
Published: April 2010

Abstract. Atmospheric hydrogen (H2) mixing ratios were observed over a one year period from summer 2007 to 2008 in Helsinki, Finland. Relatively stable background values of hydrogen were occasionally observed at the site, with minimum in October and maximum between March and May. High hydrogen mixing ratios occurred simultaneously with high carbon monoxide (CO) values and coincided with high traffic flow periods. Carbon monoxide and radon (222Rn) were continuously monitored at the same site and they were used in estimation of the hydrogen emissions from traffic. The morning rush hour slope of ΔH2/ΔCO was in average 0.43±0.03 ppb (H2)/ppb (CO). After correction due to soil deposition of H2 the slope was 0.49±0.07 ppb (H2)/ppb (CO). Using this slope and CO emission statistics, a road traffic emission of about 260 t (H2)/year was estimated for Helsinki in 2007.
Global carbon tetrachloride distributions obtained from the Atmospheric Chemistry Experiment (ACE)
Authors: Allen N. D. C. , Bernath P. F. , Boone C. D. , Chipperfield M. P. , Fu D. , Manney G. L. , Oram D. E. , Toon G. C. , Weisenstein D. K.
Published: April 2010

Abstract. The first study of the global atmospheric distribution of carbon tetrachloride (CCl4), as a function of altitude and latitude, was performed using solar occultation measurements obtained by the Atmospheric Chemistry Experiment (ACE) mission using Fourier transform spectroscopy. A total of 8703 profile measurements were taken in the upper troposphere and lower stratosphere between February 2004 and August 2007. The zonal distribution of carbon tetrachloride displays a slight hemispheric asymmetry and decreasing concentration with increasing altitude at all latitudes. Maximum carbon tetrachloride concentrations are situated below 10 km in altitude with VMR (Volume Mixing Ratio) values of 100–130 ppt (parts per trillion). The highest concentrations are located about the Equator and at mid-latitudes, particularly for latitudes in heavily industrialised regions (20–45° N), with values declining towards the poles. Global distributions obtained from ACE were compared with predictions from three chemistry transport models showing good agreement in terms of the vertical gradient despite an overall offset. The ACE dataset gives unique global and temporal coverage of carbon tetrachloride and its transport through the atmosphere. An estimated lifetime for carbon tetrachloride of 34±5 years was determined through correlation with CFC-11.
Observational study of influence of aerosol hygroscopic growth on scattering coefficient over rural area near Beijing mega-city
Authors: Pan X. L. , Yan P. , Tang J. , Ma J. Z. , Wang Z. F. , Gbaguidi A. , Sun Y. L.
Published: April 2010

Abstract. We investigated aerosol hygroscopic growth property and its influence on scattering coefficient using M9003 nephelometers in coupling with humidity controlled inlet system at a rural site near Beijing mega-city from 24 April to 15 May 2006. Inlet relative humidity was controlled in an increasing range of 40%–90% while aerosol hygroscopic growth factor of scattering coefficient, f(RH=80%) as ratio of scattering coefficient at RH=80% to "dry" scattering coefficient (RH<40%) varied in a range of 1.07–2.35 during the measurement. Further analysis indicated that under dust episode, measured f(RH=80%) is 1.2±0.02, and estimated periodic mean value of f(RH=80%) was 1.31±0.03 under clean periods; during urban pollution periods, the aerosol displayed relative strong water absorbing properties with f(RH=80%) of about 1.57±0.02. An examination of chemical composition of daily filter samples highlighted that aerosol hygroscopicity was generally depressed with the increasing ratio of organic matter (OMC)/ammonium sulfate (AS) in particle mass, similar with the results of many previous studies. However, a special case with high value of f(RH=80%)=2.21 and high OMC/AS ratio was also observed, this exception reflected physico-chemical particularities of organic matter and its complex interaction with other compounds during this episode.
Simulation of the climate impact of Mt. Pinatubo eruption using ECHAM5 – Part 1: Sensitivity to the modes of atmospheric circulation and boundary conditions
Authors: Thomas M. A. , Timmreck C. , Giorgetta M. A. , Graf H.-F. , Stenchikov G.
Published: April 2010

Abstract. The eruption of Mt. Pinatubo in the Philippines in June 1991 was one of the strongest volcanic eruptions in the 20th century and this well observed eruption can serve as an important case study to understand the subsequent weather and climate changes. In this paper, the most comprehensive simulations to date of the climate impact of Mt. Pinatubo eruption are carried out with prescribed volcanic aerosols including observed SSTs, QBO and volcanically induced ozone anomalies. This is also the first attempt to include all the known factors for the simulation of such an experiment. Here, the climate response is evaluated under different boundary conditions including one at a time, thereby, investigating the radiative and dynamical responses to individual and combined forcings by observed SSTs, QBO and volcanic effects. Two ensembles of ten members each, for unperturbed and volcanically perturbed conditions were carried out using the middle atmosphere configuration of ECHAM5 general circulation model. Our results show that the simulated climate response that may arise solely from aerosol forcing in lower stratospheric temperature is insensitive to the boundary conditions in the tropics and does not show some observed features such as the temperature signature of the QBO phases. Also, statistically significant positive anomalies in the high latitudes in NH winter of 1991/92 seen in our model simulations with prescribed observed SST and QBO phases as boundary conditions are consistent with the observations. To simulate realistically the lower stratospheric temperature response, one must include all the known factors. The pure QBO and ocean signatures in lower stratospheric temperature are simulated consistently with earlier studies. The indirect effect of the volcanic aerosols manifested as the winter warming pattern is not simulated in the ensemble mean of the experiments. Our analysis also shows that the response to El Niño conditions is very strong in the model and that it partially masks the effects due to volcanic forcing.
Closing the peroxy acetyl nitrate budget: observations of acyl peroxy nitrates (PAN, PPN, and MPAN) during BEARPEX 2007
Authors: LaFranchi B. W. , Wolfe G. M. , Thornton J. A. , Harrold S. A. , Browne E. C. , Min K. E. , Wooldridge P. J. , Gilman J. B. , Kuster W. C. , Goldan P. D. , de Gouw J. A. , McKay M. , Goldstein A. H. , Ren X. , Mao J. , Cohen R. C.
Published: April 2010

Abstract. Acyl peroxy nitrates (APNs, also known as PANs) are formed from the oxidation of aldehydes and other oxygenated VOC (oVOC) in the presence of NO2. There are both anthropogenic and biogenic oVOC precursors to APNs, but a detailed evaluation of this chemistry against observations has proven elusive. Here we describe measurements of PAN, PPN, and MPAN along with the majority of chemicals that participate in their production and loss, including OH, HO2, numerous oVOC, and NO2. Observations were made during the Biosphere Effects on AeRosols and Photochemistry Experiment (BEARPEX 2007) in the outflow of the Sacramento urban plume. These observations are used to evaluate a detailed chemical model of APN ratios and concentrations. We find that the ratios of APNs are nearly independent of the loss mechanisms and thus an especially good test of our understanding of their sources. We show that oxidation of methylvinyl ketone, methacrolein, methyl glyoxal, biacetyl and acetaldehyde are all significant sources of the PAN+peroxy acetyl (PA) radical reservoir, accounting for 26%, 2%, 7%, 20%, and 45%, of the production rate on average during the campaign, respectively. At high temperatures, when upwind isoprene emissions are highest, oxidation of non-acetaldehyde PA radical sources contributes over 60% to the total PA production rate, with methylvinyl ketone being the most important of the isoprene-derived sources. An analysis of absolute APN concentrations reveals a missing APN sink that can be resolved by increasing the PA+∑RO2 rate constant by a factor of 3.
Chemical apportionment of southern African aerosol mass and optical depth
Authors: Magi B. I.
Published: April 2010

Abstract. This study characterizes the aerosol over extratropical and tropical southern Africa during the biomass burning season by presenting an aerosol mass apportionment and aerosol optical properties. Carbonaceous aerosol species account for 54% and 83% of the extratropical and tropical aerosol mass, respectively, which is consistent with the fact that the major source of particulate matter in southern Africa is biomass burning. This mass apportionment implies that carbonaceous species in the form of organic carbon (OC) and black carbon (BC) play a critical role in the aerosol optical properties. By combining the in situ measurements of aerosol mass concentrations with concurrent measurements of aerosol optical properties at a wavelength of 550 nm, it is shown that 80–90% of the aerosol scattering is due to carbonaceous aerosol, and the derived mass scattering cross sections (MSC) for OC and BC are 3.9±0.6 m2/g and 1.6±0.2 m2/g, respectively. Derived values of mass absorption cross sections (MAC) for OC and BC are 0.7±0.6 m2/g and 8.2±1.1 m2/g, respectively. The values of MAC imply that ~26% of the aerosol absorption in southern Africa is due to OC, with the remainder due to BC. The results in this study provide important constraints for aerosol properties in a region dominated by biomass burning and should be integrated into climate models to improve aerosol simulations.
Gas phase acetic acid and its qualitative effects on snow crystal morphology and the quasi-liquid layer
Authors: Knepp T. N. , Renkens T. L. , Shepson P. B.
Published: April 2010

Abstract. A chamber was constructed within which snow crystals were grown on a string at various temperatures, relative humidities, and acetic acid gas phase mole fractions. The temperature, relative humidity, and acid mole fraction were measured for the first time at the point of crystal growth. Snow crystal morphological transition temperature shifts were recorded as a function of acid mole fraction, and interpreted according to the calculated acid concentration in the crystal's quasi-liquid layer, which is believed to have increased in thickness as a function of acid mole fraction, thereby affecting the crystal's morphology consistent with the hypothesis of Kuroda and Lacmann. Deficiencies in the understanding of the quasi-liquid layer and its role in determining snow crystal morphology are briefly discussed.
Simulation of particle size distribution with a global aerosol model: contribution of nucleation to aerosol and CCN number concentrations
Authors: Yu F. , Luo G.
Published: April 2010

Abstract. An advanced particle microphysics model with a number of computationally efficient schemes has been incorporated into a global chemistry transport model (GEOS-Chem) to simulate particle number size distributions and cloud condensation nuclei (CCN) concentrations in the atmosphere. Size-resolved microphysics for secondary particles (i.e., those formed from gaseous species) and sea salt has been treated in the present study. The growth of nucleated particles through the condensation of sulfuric acid vapor and equilibrium uptake of nitrate, ammonium, and secondary organic aerosol is explicitly simulated, along with the scavenging of secondary particles by primary particles (dust, black carbon, organic carbon, and sea salt). We calculate secondary particle formation rate based on ion-mediated nucleation (IMN) mechanism and constrain the parameterizations of primary particle emissions with various observations. Our simulations indicate that secondary particles formed via IMN appear to be able to account for the particle number concentrations observed in many parts of the troposphere. A comparison of the simulated annual mean concentrations of condensation nuclei larger than 10 nm (CN10) with those measured values show very good agreement (within a factor of two) in near all 22 sites around the globe that have at least one full year of CN10 measurements. Secondary particles appear to dominate the number abundance in most parts of the troposphere. Calculated CCN concentration at supersaturation of 0.4% (CCN0.4) and the fraction of CCN0.4 that is secondary (fsecCCN) have large spatial variations. Over the middle latitude in the Northern Hemisphere, zonally averaged CCN0.4 decreases from ~400–700 cm−3 in the boundary layer (BL) to below 100 cm−3 above altitude of ~4 km, the corresponding fsecCCN values change from 50–60% to above ~70%. In the Southern Hemisphere, the zonally averaged CCN0.4 is below 200 cm−3 and fsecCCN is generally above 60% except in the BL over the Southern Ocean.
Rates and regimes of photochemical ozone production over Central East China in June 2006: a box model analysis using comprehensive measurements of ozone precursors
Authors: Kanaya Y. , Pochanart P. , Liu Y. , Li J. , Tanimoto H. , Kato S. , Suthawaree J. , Inomata S. , Taketani F. , Okuzawa K. , Kawamura K. , Akimoto H. , Wang Z. F.
Published: April 2010

Abstract. An observation-based box model approach was undertaken to estimate concentrations of OH, HO2, and RO2 radicals and the net photochemical production rate of ozone at the top of Mount Tai, located in the middle of Central East China, in June 2006. The model calculation was constrained by the measurements of O3, H2O, CO, NO, NO2, hydrocarbon, HCHO, and CH3CHO concentrations, and temperature and J values. The net production rate of ozone was estimated to be 6.4 ppb h−1 as a 6-h average (09:00–15:00 CST), suggesting 58±37 ppb of ozone is produced in one day. Thus the daytime buildup of ozone recorded at the mountain top as ~23 ppb on average is likely affected by in situ photochemistry as well as by the upward transport of polluted air mass in the daytime. On days with high ozone concentrations (hourly values exceeding 100 ppb at least once), in situ photochemistry was more active than it was on low ozone days, suggesting that in situ photochemistry is an important factor controlling ozone concentrations. Sensitivity model runs for which different NOx and hydrocarbon concentrations were assumed suggested that the ozone production occurred normally under NOx-limited conditions, with some exceptional periods (under volatile-organic-compound-limited conditions) in which there was fresh pollution. We also examined the possible influence of the heterogeneous loss of gaseous HO2 radicals in contact with aerosol particle surfaces on the rate and regimes of ozone production.
Kinetic modeling of nucleation experiments involving SO2 and OH: new insights into the underlying nucleation mechanisms
Authors: Du H. , Yu F.
Published: April 2010

Abstract. Nucleation is an important source of atmospheric aerosols which have significant climatic and health implications. Despite intensive theoretical and field studies over the past decades, the dominant nucleation mechanism in the lower troposphere remains to be mysterious. Several recent laboratory studies on atmospheric nucleation may shed light on this important problem. However, the most interesting finding from those studies was based on the derived H2SO4 concentration whose accuracy has not yet been evaluated by any other means. Moreover, the threshold H2SO4 concentration needed to reach the same degree of nucleation reported by two separate nucleation studies varies by about one order of magnitude. In this study, we apply a recently updated kinetic nucleation model to study the nucleation phenomena observed in those recent experiments. We show that the H2SO4 concentration can be estimated with a higher level of accuracy with the kinetic model by constraining the simulated particle size distributions with observed ones. We find that the required H2SO4 concentrations to achieve the best agreement between modeling and measurements are a factor of ~2 to 4 higher than reported in those experiments. More importantly, by comparing the derived thermodynamic properties associated with the nucleation process, we conclude that different unknown species may participate in the two separate nucleation experimental studies, which may explain the large difference in the reported threshold H2SO4 concentration. Although the unknown species involved has yet to be identified, the derived values of thermodynamic properties can serve as a valuable guideline for the search of their chemical identities using advanced quantum-chemical approaches.