bluuebunny/crossref_metadata_2025 huggingface dataset:
Measurements of aerosol absorption and scattering in the Mexico City Metropolitan Area during the MILAGRO field campaign: a comparison of results from the T0 and T1 sites
Authors: Marley N. A. , Gaffney J. S. , Castro T. , Salcido A. , Frederick J.
Published: April 2010

Abstract. In March 2006, a multiagency field campaign was undertaken in Mexico City called the Megacities Initiative: Local and Global Research Observations (MILAGRO). Two of the five field components of the MILAGRO study focused a major part of their efforts on atmospheric particulate emissions from the Mexico City basin and their effects on radiative balance as a function of time, location and processing conditions. As part of these two MILAGRO components, measurements of aerosol optical properties were obtained at a site located in the northern part of Mexico City (T0) and also at a site located 29 km northwest (T1) to estimate the regional effects of aerosol emissions from the basin. Measurements of aerosol absorption and scattering for fine mode aerosols were obtained at both sites. Aerosol absorption at 550 nm was similar at both sites, ranging from 7–107 Mm−1 at T0 and from 3–147 Mm−1 at T1. Aerosol scattering measured at 550 nm at T0 ranged from 16–344 Mm−1 while the aerosol scattering values at T1 were much lower than at T0 ranging from 2–136 Mm−1. Aerosol single scattering albedos (SSAs) were calculated at 550 nm for the fine mode aerosols at both sites using these data. The SSAs at T0 ranged from 0.47–0.92 while SSAs at T1 ranged from 0.35–0.86. The presence of these highly absorbing fine aerosols in the lower atmosphere of the Mexico City area will result in a positive climate forcing and a local warming of the boundary layer in the region. Broadband UVB intensity was found to be higher at site T0, with an average of 64 μW/cm2 at solar noon, than at site T1, which had an average of 54 μW/cm2 at solar noon. Comparisons of clear-sky modeled UVB intensities with the simultaneous UVB measurements obtained at sites T0 and T1 for cloudless days indicate a larger diffuse radiation field at site T0 than at site T1. The determination of aerosol Ångstrom scattering coefficients at T0 suggests that this is due to the predominance of aerosols in the size range of 0.3 micron, which leads to scattering of UVB radiation peaked in the forward direction and to an enhanced UVB radiation observed at ground level. This enhancement of the UVB diffuse radiation field would explain the enhanced photochemistry observed in the Mexico City area despite the reduction in UVB anticipated from light absorbing species.
Gaseous mercury distribution in the upper troposphere and lower stratosphere observed onboard the CARIBIC passenger aircraft
Authors: Slemr F. , Ebinghaus R. , Brenninkmeijer C. A. M. , Hermann M. , Kock H. H. , Martinsson B. G. , Schuck T. , Sprung D. , van Velthoven P. , Zahn A. , Ziereis H.
Published: April 2010

Abstract. Total gaseous mercury (TGM) was measured onboard a passenger aircraft during monthly CARIBIC flights (Civil Aircraft for Regular Investigation of the Atmosphere Based on an Instrumented Container) made between May 2005 and March 2007 on the routes Frankfurt–São Paulo–Santiago de Chile and back and Frankfurt–Guangzhou–Manila and back. The data provide for the first time an insight into the seasonal distributions of TGM in the upper troposphere and lower stratosphere (UT/LS) of both hemispheres and demonstrate the importance of mercury emissions from biomass burning in the Southern Hemisphere. Numerous plumes were observed in the upper troposphere, the larger of which could be characterized in terms of Hg/CO emission ratios and their probable origins. During the flights to China TGM correlated with CO in the upper troposphere with a seasonally dependent slope reflecting the longer lifetime of elemental mercury when compared to that of CO. A pronounced depletion of TGM was always observed in the extratropical lowermost stratosphere. TGM concentrations there were found to decrease with the increasing concentrations of particles. Combined with the large concentrations of particle bond mercury in the stratosphere observed by others, this finding suggests either a direct conversion of TGM to particle bound mercury or an indirect conversion via a semivolatile bivalent mercury compound. Based on concurrent measurements of SF6 during two flights, the rate of this conversion is estimated to 0.4 ng m−3 yr−1. A zero TGM concentration was not observed during some 200 flight hours in the lowermost stratosphere suggesting an equilibrium between the gaseous and particulate mercury.
Carbonaceous aerosols in Norwegian urban areas
Authors: Yttri K. E. , Dye C. , Braathen O.-A. , Simpson D. , Steinnes E.
Published: April 2010

Abstract. Little is known regarding levels and source strength of carbonaceous aerosols in Scandinavia. In the present study, ambient aerosol (PM10 and PM2.5) concentrations of elemental carbon (EC), organic carbon (OC), water-insoluble organic carbon (WINSOC), and water-soluble organic carbon (WSOC) are reported for a curbside site, an urban background site, and a suburban site in Norway in order to investigate their spatial and seasonal variations. Aerosol filter samples were collected using tandem filter sampling to correct for the positive sampling artefact introduced by volatile and semivolatile OC. Analyses were performed using the thermal optical transmission (TOT) instrument from Sunset Lab Inc., which corrects for charring during analysis. Finally, we estimated the relative contribution of OC from wood burning based on the samples content of levoglucosan. Levels of EC varied by more than one order of magnitude between sites, likely due to the higher impact of vehicular traffic at the curbside and the urban background sites. In winter, the level of particulate organic carbon (OCp) at the suburban site was equal to (for PM10) or even higher (for PM2.5) than the levels observed at the curbside and the urban background sites. This finding was attributed to the impact of residential wood burning at the suburban site in winter, which was confirmed by a high mean concentration of levoglucosan (407 ng m−3). This finding indicates that exposure to primary combustion derived OCp could be equally high in residential areas as in a city center. It is demonstrated that OCp from wood burning (OCwood) accounted for almost all OCp at the suburban site in winter, allowing a new estimate of the ratio TCp/levoglucosan for both PM10 and PM2.5. Particulate carbonaceous material (PCM=Organic matter+Elemental matter) accounted for 46–83% of PM10 at the sites studied, thus being the major fraction.
Secondary organic aerosol formation from primary aliphatic amines with NO3 radical
Authors: Malloy Q. G. J. ,   Li Qi, Warren B. , Cocker III D. R. , Erupe M. E. , Silva P. J.
Published: April 2010

Abstract. Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine) are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (<1% for all amines tested) as detected by an aerosol mass spectrometer (AMS). We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.
Thermodynamic characterization of Mexico City aerosol during MILAGRO 2006
Authors: Fountoukis C. , Nenes A. , Sullivan A. , Weber R. , Van Reken T. , Fischer M. , Matías E. , Moya M. , Farmer D. , Cohen R. C.
Published: April 2010

Abstract. Fast measurements of aerosol and gas-phase constituents coupled with the ISORROPIA-II thermodynamic equilibrium model are used to study the partitioning of semivolatile inorganic species and phase state of Mexico City aerosol sampled at the T1 site during the MILAGRO 2006 campaign. Overall, predicted semivolatile partitioning agrees well with measurements. PM2.5 is insensitive to changes in ammonia but is to acidic semivolatile species. For particle sizes up to 1μm diameter, semi-volatile partitioning requires 15–30 min to equilibrate; longer time is typically required during the night and early morning hours. Aerosol and gas-phase speciation always exhibits substantial temporal variability, so that aerosol composition measurements (bulk or size-resolved) obtained over large integration periods are not reflective of its true state. When the aerosol sulfate-to-nitrate molar ratio is less than unity, predictions improve substantially if the aerosol is assumed to follow the deliquescent phase diagram. Treating crustal species as "equivalent sodium" (rather than explicitly) in the thermodynamic equilibrium calculations introduces important biases in predicted aerosol water uptake, nitrate and ammonium; neglecting crustals further increases errors dramatically. This suggests that explicitly considering crustals in the thermodynamic calculations is required to accurately predict the partitioning and phase state of aerosols.
Validation of an experimental setup to study atmospheric heterogeneous ozonolysis of semi-volatile organic compounds
Authors: Pflieger M. , Goriaux M. , Temime-Roussel B. , Gligorovski S. , Monod A. , Wortham H.
Published: April 2010

Abstract. There is currently a need for reliable experimental procedures to follow the heterogeneous processing simulating the atmospheric conditions. This work offers an alternative experimental device to study the behaviour of semi-volatile organic compounds (SVOC) that presumably exhibit extremely slow reactivity (e.g. pesticides) towards the atmospheric oxidants such as ozone and OH. Naphthalene was chosen as a test compound since it was widely studied in the past and hence represents a good reference. Prior to ozone exposure, the gaseous naphthalene was adsorbed via gas-solid equilibrium on silica and XAD-4 particles. Then, the heterogeneous reaction of ozone with adsorbed naphthalene was investigated in specially designed flow tube reactors. After the reaction, the remaining naphthalene (adsorbed on particles surface) was extracted, filtered and analyzed by Gas Chromatography-Flame Ionization Detector (GC-FID). Thus, the kinetics results were obtained following the consumption of naphthalene. Using this procedure, the rate constants of heterogeneous ozonolysis of naphthalene (kO3 silica=2.26 (±0.09)×10−17 cm3 molec−1 s−1 and kO3 XAD-4=4.29 (±1.06)×10−19 cm3 molec−1 s−1) were determined for silica and XAD-4 particles, at 25°C and relative humidity <0.7%. The results show that the nature of the particles significantly affects the kinetics and that heterogeneous ozonolysis of naphthalene is faster than its homogeneous ozonolysis in the gas phase.
Carbon monoxide distributions from the upper troposphere to the mesosphere inferred from 4.7 μm non-local thermal equilibrium emissions measured by MIPAS on Envisat
Authors: Funke B. , López-Puertas M. , García-Comas M. , Stiller G. P. , von Clarmann T. , Höpfner M. , Glatthor N. , Grabowski U. , Kellmann S. , Linden A.
Published: April 2010

Abstract. We present global distributions of carbon monoxide (CO) from the upper troposphere to the mesosphere observed by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on Envisat. Vertically resolved volume mixing ratio profiles have been retrieved from 4.7 μm limb emission spectra under consideration of non-local thermodynamic equilibrium. The precision of individual CO profiles is typically 5–30 ppbv (15–40% for altitudes greater than 40 km and lower than 15 km and 30–90% within 15–40 km). Estimated systematic errors are in the order of 8–15%. Below 60 km, the vertical resolution is 4–7 km. The data set which covers 54 days from September 2003 to March 2004 has been derived with an improved retrieval version including (i) the retrieval of log(vmr), (ii) the consideration of illumination-dependent vibrational population gradients along the instrument's line of sight, and (iii) joint-fitted vmr horizontal gradients in latitudinal and longitudinal directions. A detailed analysis of spatially resolved CO distributions during the 2003/2004 Northern Hemisphere major warming event demonstrate the potential of MIPAS CO observations to obtain new information on transport processes during dynamical active episodes, particularly on those acting in the vertical. From the temporal evolution of zonally averaged CO abundances, we derived extraordinary polar winter descent velocities of 1200 m per day inside the recovered polar vortex in January 2004. Middle stratospheric CO abundances show a well established correlation with the chemical source CH4, particularly in the tropics. In the upper troposphere, a moderate CO decrease from September 2003 to March 2004 was observed. Upper tropospheric CO observations provide a detailed picture of long-range transport of polluted air masses and uplift events. MIPAS observations taken on 9–11 September 2003 confirm the trapping of convective outflow of polluted CO-rich air from Southeast Asia into the Asian monsoon anticyclone, which has been described in previous studies. Upper tropospheric CO plumes, observed by MIPAS on this day, were predominantly located in the Northern Hemisphere. Most of these plumes could be related to Southeast Asian pollution by means of backward trajectory calculations. During 20–22 October, southern hemispheric biomass burning was the most likely source of the major CO plumes observed over the Southern Atlantic and Indian Ocean.
Impact of primary formaldehyde on air pollution in the Mexico City Metropolitan Area
Authors: Lei W. , Zavala M. , de Foy B. , Volkamer R. , Molina M. J. , Molina L. T.
Published: April 2010

Abstract. Formaldehyde (HCHO) is a radical source that plays an important role in urban atmospheric chemistry and ozone formation. The Mexico City Metropolitan Area (MCMA) is characterized by high anthropogenic emissions of HCHO (primary HCHO), which together with photochemical production of HCHO from hydrocarbon oxidation (secondary HCHO), lead to high ambient HCHO levels. The CAMx chemical transport model was employed to evaluate the impact of primary HCHO on its ambient concentration, on the ROx radical budget, and on ozone (O3) formation in the MCMA. Important radical sources, including HCHO, HONO, and O3-olefin reactions, were constrained by measurements from routine observations of the local ambient air monitoring network and the MCMA-2003 field campaign. Primary HCHO was found not only to contribute significantly to the ambient HCHO concentration, but also to enhance the radical budget and O3 production in the urban atmosphere of the MCMA. Overall in the urban area, total daytime radical production is enhanced by up to 10% and peak O3 concentration by up to 8%; moreover primary HCHO tends to make O3 both production rates and ambient concentration peak half an hour earlier. While primary HCHO contributes predominantly to the ambient HCHO concentration between nighttime and morning rush hours, significant influence on the radical budget and O3 production starts early in the morning, peaks at mid-morning and is sustained until early afternoon.
Microphysical and radiative characterization of a subvisible midlevel Arctic ice cloud by airborne observations – a case study
Authors: Lampert A. , Ehrlich A. , Dörnbrack A. , Jourdan O. , Gayet J.-F. , Mioche G. , Shcherbakov V. , Ritter C. , Wendisch M.
Published: April 2010

Abstract. During the Arctic Study of Tropospheric Aerosol, Clouds and Radiation (ASTAR) campaign, which was conducted in March and April 2007, an optically thin ice cloud was observed south of Svalbard at around 3 km altitude. The microphysical and radiative properties of this particular subvisible midlevel cloud were investigated with complementary remote sensing and in situ instruments. Collocated airborne lidar remote sensing and spectral solar radiation measurements were performed at a flight altitude of 2300 m below the cloud base. Under almost stationary atmospheric conditions, the same subvisible midlevel cloud was probed with various in situ sensors roughly 30 min later. From individual ice crystal samples detected with the Cloud Particle Imager and the ensemble of particles measured with the Polar Nephelometer, microphysical properties were retrieved with a bi-modal inversion algorithm. The best agreement with the measurements was obtained for small ice spheres and deeply rough hexagonal ice crystals. Furthermore, the single-scattering albedo, the scattering phase function as well as the volume extinction coefficient and the effective diameter of the crystal population were determined. A lidar ratio of 21(±6) sr was deduced by three independent methods. These parameters in conjunction with the cloud optical thickness obtained from the lidar measurements were used to compute spectral and broadband radiances and irradiances with a radiative transfer code. The simulated results agreed with the observed spectral downwelling radiance within the range given by the measurement uncertainty. Furthermore, the broadband radiative simulations estimated a net (solar plus thermal infrared) radiative forcing of the subvisible midlevel ice cloud of −0.4 W m−2 (−3.2 W m−2 in the solar and +2.8 W m−2 in the thermal infrared wavelength range).
Anthropogenic influence on SOA and the resulting radiative forcing
Authors: Hoyle C. R. , Myhre G. , Berntsen T. K. , Isaksen I. S. A.
Published: April 2010

Abstract. The effect of chemical changes in the atmosphere since the pre-industrial period on the distributions and burdens of Secondary Organic Aerosol (SOA) has been calculated using the off-line aerosol chemistry transport model Oslo CTM2. The production of SOA was found to have increased from about 35 Tg yr−1 to 53 Tg yr−1 since pre-industrial times, leading to an increase in the global annual mean SOA burden from 0.33 Tg to 0.50 Tg, or about 51%. The effect of allowing semi-volatile species to partition to sulphate aerosol was also tested, leading to an increase in SOA production from about 43 Tg yr−1 to 69 Tg yr−1 since pre-industrial times, while the annual mean SOA burden increased from 0.44 Tg to 0.70 Tg, or about 59%. The increases were greatest over industrialised areas, especially when partitioning to sulphate aerosol was allowed, as well as over regions with high biogenic precursor emissions. The contribution of emissions from different sources to the larger SOA burdens has been calculated. The results suggest that the majority of the increase was caused by emissions of primary organic aerosols (POA), from fossil fuel and bio fuel combustion. As yet, very few radiative forcing estimates of SOA exist, and no such estimates were provided in the latest IPCC report. In this study, we found that the change in SOA burden caused a radiative forcing (defined here as the difference between the pre-industrial and the present day run) of −0.09 W m−2, when SOA was allowed to partition to both organic and sulphate aerosols, and −0.06 W m−2 when only partitioning to organic aerosols was assumed. Therefore, the radiative forcing of SOA was found to be stronger than the best estimate for POA in the latest IPCC assessment.
Simulation of the climate impact of Mt. Pinatubo eruption using ECHAM5 – Part 2: Sensitivity to the phase of the QBO and ENSO
Authors: Thomas M. A. , Giorgetta M. A. , Timmreck C. , Graf H.-F. , Stenchikov G.
Published: April 2010

Abstract. The sensitivity of the climate impact of Mt. Pinatubo eruption in the tropics and extratropics to different QBO phases is investigated. Mt. Pinatubo erupted in June 1991 during the easterly phase of the QBO at 30 hPa and the phase change to westerly took place in August 1992. Here, the consequences are analyzed if the QBO phase had been in the opposite phase during the eruption of Mt. Pinatubo. Hence, in this study, simulations are carried out using the middle atmosphere configuration of ECHAM5 general circulation model for two cases – one with the observed QBO phase and the other with the opposite QBO phase. The response of temperature and geopotential height in the lower stratosphere is evaluated for the following cases – (1) when only the effects of the QBO are included and (2) when the effects of aerosols, QBO and SSTs (combined response) are included. The tropical QBO signature in the lower stratospheric temperature is well captured in the pure QBO responses and in the combined (aerosol + ocean + QBO) responses. The response of the extratropical atmosphere to the QBO during the second winter after the eruption is captured realistically in the case of the combined forcing showing a strengthening of the polar vortex when the QBO is in its westerly phase and a warm, weak polar vortex in the easterly QBO phase. The vortex is disturbed during the first winter irrespective of the QBO phases in the combined responses and this may be due to the strong influences of El Niño during the first winters after eruption. However, the pure QBO experiments do not realistically reproduce a strengthening of the polar vortex in the westerly QBO phase, even though below normal temperatures in the high latitudes are seen in October-November-December months when the opposite QBO phase is prescribed instead of the December-January-February winter months used here for averaging.
Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol
Authors: Brown S. S. , deGouw J. A. , Warneke C. , Ryerson T. B. , Dubé W. P. , Atlas E. , Weber R. J. , Peltier R. E. , Neuman J. A. , Roberts J. M. , Swanson A. , Flocke F. , McKeen S. A. , Brioude J. , Sommariva R. , Trainer M. , Fehsenfeld F. C. , Ravishankara A. R.
Published: April 2010

Abstract. Isoprene is the largest single VOC emission to the atmosphere. Although it is primarily oxidized photochemically during daylight hours, late-day emissions that remain in the atmosphere at sunset undergo oxidation by NO3 in regionally polluted areas with large NOx levels. A recent aircraft study examined isoprene and its nocturnal oxidants in a series of night flights across the Northeast US, a region with large emissions of both isoprene and NOx. Substantial amounts of isoprene that were observed after dark were strongly anticorrelated with measured NO3 and were the most important factor determining the lifetime of this radical. The products of photochemical oxidation of isoprene, methyl vinyl ketone and methacrolein, were more uniformly distributed, and served as tracers for the presence of isoprene at sunset, prior to its oxidation by NO3. A determination of the mass of isoprene oxidized in darkness showed it to be a large fraction (>20%) of emitted isoprene. Organic nitrates produced from the NO3+isoprene reaction, though not directly measured, were estimated to account for 2–9% of total reactive nitrogen. The mass of isoprene oxidized by NO3 was comparable to and correlated with the organic aerosol loading for flights with relatively low organic aerosol background. The contribution of nocturnal isoprene oxidation to secondary organic aerosol was determined in the range 1–17%, and isoprene SOA mass derived from NO3 was calculated to exceed that due to OH by approximately 50%.
Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs)
Authors: Chan A. W. H. , Kautzman K. E. , Chhabra P. S. , Surratt J. D. , Chan M. N. , Crounse J. D. , Kürten A. , Wennberg P. O. , Flagan R. C. , Seinfeld J. H.
Published: April 2010

Abstract. Current atmospheric models do not include secondary organic aerosol (SOA) production from gas-phase reactions of polycyclic aromatic hydrocarbons (PAHs). Recent studies have shown that primary emissions undergo oxidation in the gas phase, leading to SOA formation. This opens the possibility that low-volatility gas-phase precursors are a potentially large source of SOA. In this work, SOA formation from gas-phase photooxidation of naphthalene, 1-methylnaphthalene (1-MN), 2-methylnaphthalene (2-MN), and 1,2-dimethylnaphthalene (1,2-DMN) is studied in the Caltech dual 28-m3 chambers. Under high-NOx conditions and aerosol mass loadings between 10 and 40 μg m−3, the SOA yields (mass of SOA per mass of hydrocarbon reacted) ranged from 0.19 to 0.30 for naphthalene, 0.19 to 0.39 for 1-MN, 0.26 to 0.45 for 2-MN, and constant at 0.31 for 1,2-DMN. Under low-NOx conditions, the SOA yields were measured to be 0.73, 0.68, and 0.58, for naphthalene, 1-MN, and 2-MN, respectively. The SOA was observed to be semivolatile under high-NOx conditions and essentially nonvolatile under low-NOx conditions, owing to the higher fraction of ring-retaining products formed under low-NOx conditions. When applying these measured yields to estimate SOA formation from primary emissions of diesel engines and wood burning, PAHs are estimated to yield 3–5 times more SOA than light aromatic compounds over photooxidation timescales of less than 12 h. PAHs can also account for up to 54% of the total SOA from oxidation of diesel emissions, representing a potentially large source of urban SOA.
A simulation of the global distribution and radiative forcing of soil dust aerosols at the Last Glacial Maximum
Authors: Takemura T. , Egashira M. , Matsuzawa K. , Ichijo H. , O'ishi R. , Abe-Ouchi A.
Published: April 2010

Abstract. In this study an integrated simulation of the global distribution and the radiative forcing of soil dust aerosols at the Last Glacial Maximum (LGM) is performed with an aerosol climate model, SPRINTARS. It is compared with another simulation for the present climate condition. The global total emission flux of soil dust aerosols at the LGM is simulated to be about 2.4 times as large as that in the present climate, and the simulated deposition flux is in general agreement with estimations from ice core and marine sediment samplings though it appears to be underestimated over the Antarctic. The calculated direct radiative forcings of soil dust aerosols at the LGM is close to zero at the tropopause and −0.4 W m−2 at the surface. These radiative forcings are about twice as large as those in the present climate. SPRINTARS also includes the microphysical parameterizations of the cloud-aerosol interaction both for liquid water and ice crystals, which affect the radiation budget. The positive radiative forcing from the indirect effect of soil dust aerosols is mainly caused by their properties to act as ice nuclei. This effect is simulated to be smaller (−0.9 W m−2) at the LGM than in the present. It is suggested that atmospheric dust might contribute to the cold climate during the glacial periods both through the direct and indirect effects, relative to the interglacial periods.
Trans-pacific dust transport: integrated analysis of NASA/CALIPSO and a global aerosol transport model
Authors: Eguchi K. , Uno I. , Yumimoto K. , Takemura T. , Shimizu A. , Sugimoto N. , Liu Z.
Published: April 2010

Abstract. Detailed 3-D structures of Trans-Pacific Asian dust transport occurring during 5–15 May 2007 were investigated using the NASA/CALIOP vertical-resolved measurements and a three-dimensional aerosol model (SPRINTARS). Both CALIOP and SPRINTARS dust extinctions showed a good agreement along the way of the transport from the dust source regions across North Pacific into North America. A vertically two-layered dust distribution was observed over the northeastern Pacific and North America. The lower dust layer originated from a dust storm generated in the Gobi Desert on 5 May. It was transported at an altitude of around 4 km MSL and has mixed with Asian anthropogenic air pollutants during the course of transport. The upper dust layer mainly originated from a dust storm that occurred in the Taklimakan Desert 2–3 days after the Gobi dust storm generation. The upper dust cloud was transported in higher altitudes above the major clouds layer during the Trans-Pacific transport. It therefore has remained unmixed with the Asian air pollutants and almost unaffected by wet removal. The decay of its concentration level was small (only one-half after its long-distance transport crossing the Pacific). Our dust budget analysis revealed that the Asian dust flux passing through the longitude plane of 140° E was 2.1 Tg, and one third of that arrived North America. The cases analyzed in this study revealed that, while the Gobi Desert is an important source that can contribute to the long-range dust transport, the Taklimakan Desert appears to be another important source that can contribute to the dust transport occurring particularly at high altitudes.
The heterogeneous reaction of hydroxyl radicals with sub-micron squalane particles: a model system for understanding the oxidative aging of ambient aerosols
Authors: Smith J. D. , Kroll J. H. , Cappa C. D. , Che D. L. , Liu C. L. , Ahmed M. , Leone S. R. , Worsnop D. R. , Wilson K. R.
Published: April 2010

Abstract. The heterogeneous reaction of OH radicals with sub-micron squalane particles, in the presence of O2, is used as a model system to explore the fundamental chemical mechanisms that control the oxidative aging of organic aerosols in the atmosphere. Detailed kinetic measurements combined with elemental mass spectrometric analysis reveal that the reaction proceeds sequentially by adding an average of one oxygenated functional group per reactive loss of squalane. The reactive uptake coefficient of OH with squalane particles is determined to be 0.3±0.07 at an average OH concentration of ~1×1010 molecules cm−3. Based on a comparison between the measured particle mass and model predictions it appears that significant volatilization of a reduced organic particle would be extremely slow in the real atmosphere. However, as the aerosols become more oxygenated, volatilization becomes a significant loss channel for organic material in the particle-phase. Together these results provide a chemical framework in which to understand how heterogeneous chemistry transforms the physiochemical properties of particle-phase organic matter in the troposphere.
Evidence of mineral dust altering cloud microphysics and precipitation
Authors: Min Q.-L. , Li R. , Lin B. , Joseph E. , Wang S. , Hu Y. , Morris V. , Chang F.
Published: April 2010

Abstract. Multi-platform and multi-sensor observations are employed to investigate the impact of mineral dust on cloud microphysical and precipitation processes in mesoscale convective systems. For a given convective strength, small hydrometeors were more prevalent in the stratiform rain regions with dust than in those regions that were dust free. Evidence of abundant cloud ice particles in the dust sector, particularly at altitudes where heterogeneous nucleation of mineral dust prevails, further supports the observed changes of precipitation. The consequences of the microphysical effects of the dust aerosols were to shift the precipitation size spectrum from heavy precipitation to light precipitation and ultimately suppressing precipitation.
Effect of chemical mixing state on the hygroscopicity and cloud nucleation properties of calcium mineral dust particles
Authors: Sullivan R. C. , Moore M. J. K. , Petters M. D. , Kreidenweis S. M. , Roberts G. C. , Prather K. A.
Published: April 2010

Abstract. Atmospheric mineral dust particles can alter cloud properties and thus climate by acting as cloud condensation nuclei (CCN) that form cloud droplets. The CCN activation properties of various calcium mineral dust particles were studied experimentally to investigate the consequences of field observations showing the segregation of sulphate from nitrate and chloride between individual aged Asian dust particles, and the enrichment of oxalic acid in Asian dust. Each mineral's observed apparent hygroscopicity was primarily controlled by its solubility, which determines the degree to which the mineral's intrinsic hygroscopicity can be expressed. The significant increase in hygroscopicity caused by mixing soluble hygroscopic material with insoluble mineral particles is also presented. Insoluble minerals including calcium carbonate, representing fresh unprocessed dust, and calcium sulphate, representing atmospherically processed dust, had similarly small apparent hygroscopicities. Their activation is accurately described by a deliquescence limit following the Kelvin effect and corresponded to an apparent single-hygroscopicity parameter, κ, of ~0.001. Soluble calcium chloride and calcium nitrate, representing atmospherically processed mineral dust particles, were much more hygroscopic, activating similar to ammonium sulphate with κ~0.5. Calcium oxalate monohydrate (κ=0.05) was significantly less CCN-active than oxalic acid (κ=0.3), but not as inactive as its low solubility would predict. These results indicate that the common assumption that all mineral dust particles become more hygroscopic and CCN-active after atmospheric processing should be revisited. Calcium sulphate and calcium oxalate are two realistic proxies for aged mineral dust that remain non-hygroscopic. The dust's apparent hygroscopicity will be controlled by its chemical mixing state, which is determined by its mineralogy and the chemical reaction pathways it experiences during transport.
Applying the Condensation Particle Counter Battery (CPCB) to study the water-affinity of freshly-formed 2–9 nm particles in boreal forest
Authors: Riipinen I. , Manninen H. E. , Yli-Juuti T. , Boy M. , Sipilä M. , Ehn M. , Junninen H. , Petäjä T. , Kulmala M.
Published: April 2010

Abstract. Measurements on the composition of nanometer-sized atmospheric particles are the key to understand which vapors participate in the secondary aerosol formation processes. Knowledge on these processes is crucial in assessing the climatic effects of secondary aerosol formation. We present data of >2 nm particle concentrations and their water-affinity measured with the Condensation Particle Counter Battery (CPCB) at a boreal forest site in Hyytiälä, Finland, during spring 2006. The data reveal that during new particle formation events, the smallest particles activate for growth at clearly smaller sizes in water than in butanol vapor. However, even at 2–4 nm, there are days when the particles seem to be less hygroscopic than ammonium sulfate or sulfuric acid, which are often referred to as the most likely compounds present in atmospheric nucleation. This observation points to the possible presence of water-soluble organics, even at the very first steps on particle formation. The water-affinity of the particles decreases with size, indicating that the vapors that participate in the first steps of the particle formation and growth are more hygroscopic than the vapors contributing to the later stages of the growth. This suggests that the relative role of less hygroscopic organics in atmospheric particle growth increases as a function of particle size.
Glyoxal uptake on ammonium sulphate seed aerosol: reaction products and reversibility of uptake under dark and irradiated conditions
Authors: Galloway M. M. , Chhabra P. S. , Chan A. W. H. , Surratt J. D. , Flagan R. C. , Seinfeld J. H. , Keutsch F. N.
Published: April 2010

Abstract. Chamber studies of glyoxal uptake onto ammonium sulphate aerosol were performed under dark and irradiated conditions to gain further insight into processes controlling glyoxal uptake onto ambient aerosol. Organic fragments from glyoxal dimers and trimers were observed within the aerosol under dark and irradiated conditions. Glyoxal monomers and oligomers were the dominant organic compounds formed under the conditions of this study; glyoxal oligomer formation and overall organic growth were found to be reversible under dark conditions. Analysis of high-resolution time-of-flight aerosol mass spectra provides evidence for irreversible formation of carbon-nitrogen (C-N) compounds in the aerosol. We have identified 1H-imidazole-2-carboxaldehyde as one C-N product. To the authors' knowledge, this is the first time C-N compounds resulting from condensed phase reactions with ammonium sulphate seed have been detected in aerosol. Organosulphates were not detected under dark conditions. However, active photochemistry was found to occur within aerosol during irradiated experiments. Carboxylic acids and organic esters were identified within the aerosol. An organosulphate, which had been previously assigned as glyoxal sulphate in ambient samples and chamber studies of isoprene oxidation, was observed only in the irradiated experiments. Comparison with a laboratory synthesized standard and chemical considerations strongly suggest that this organosulphate is glycolic acid sulphate, an isomer of the previously proposed glyoxal sulphate. Our study shows that reversibility of glyoxal uptake should be taken into account in SOA models and also demonstrates the need for further investigation of C-N compound formation and photochemical processes, in particular organosulphate formation.
Source apportionment of elevated wintertime PAHs by compound-specific radiocarbon analysis
Authors: Sheesley R. J. , Kruså M. , Krecl P. , Johansson C. , Gustafsson Ö.
Published: April 2010

Abstract. Natural abundance radiocarbon analysis facilitates distinct source apportionment between contemporary biomass/biofuel (14C "alive") versus fossil fuel (14C "dead") combustion. Here, the first compound-specific radiocarbon analysis (CSRA) of atmospheric polycyclic aromatic hydrocarbons (PAHs) was demonstrated for a set of samples collected in Lycksele, Sweden a small town with frequent episodes of severe atmospheric pollution in the winter. Renewed interest in using residential wood combustion (RWC) means that this type of seasonal pollution is of increasing concern in many areas. Five individual/paired PAH isolates from three pooled fortnight-long filter collections were analyzed by CSRA: phenanthrene, fluoranthene, pyrene, benzo[b+k]fluoranthene and indeno[cd]pyrene plus benzo[ghi]perylene; phenanthrene was the only compound also analyzed in the gas phase. The measured Δ14C for PAHs spanned from −138.3‰ to 58.0‰. A simple isotopic mass balance model was applied to estimate the fraction biomass (fbiomass) contribution, which was constrained to 71–87% for the individual PAHs. Indeno[cd]pyrene plus benzo[ghi]perylene had an fbiomass of 71%, while fluoranthene and phenanthrene (gas phase) had the highest biomass contribution at 87%. The total organic carbon (TOC, defined as carbon remaining after removal of inorganic carbon) fbiomass was estimated to be 77%, which falls within the range for PAHs. This CSRA data of atmospheric PAHs established that RWC is the dominating source of atmospheric PAHs to this region of the boreal zone with some variations among RWC contributions to specific PAHs.
Emission and chemistry of organic carbon in the gas and aerosol phase at a sub-urban site near Mexico City in March 2006 during the MILAGRO study
Authors: de Gouw J. A. , Welsh-Bon D. , Warneke C. , Kuster W. C. , Alexander L. , Baker A. K. , Beyersdorf A. J. , Blake D. R. , Canagaratna M. , Celada A. T. , Huey L. G. , Junkermann W. , Onasch T. B. , Salcido A. , Sjostedt S. J. , Sullivan A. P. , Tanner D. J. , Vargas O. , Weber R. J. , Worsnop D. R. , Yu X. Y. , Zaveri R.
Published: April 2010

Abstract. Volatile organic compounds (VOCs) and carbonaceous aerosol were measured at a sub-urban site near Mexico City in March of 2006 during the MILAGRO study (Megacity Initiative: Local and Global Research Objectives). Diurnal variations of hydrocarbons, elemental carbon (EC) and hydrocarbon-like organic aerosol (HOA) were dominated by a high peak in the early morning when local emissions accumulated in a shallow boundary layer, and a minimum in the afternoon when the emissions were diluted in a significantly expanded boundary layer and, in case of the reactive gases, removed by OH. In comparison, diurnal variations of species with secondary sources such as the aldehydes, ketones, oxygenated organic aerosol (OOA) and water-soluble organic carbon (WSOC) stayed relatively high in the afternoon indicating strong photochemical formation. Emission ratios of many hydrocarbon species relative to CO were higher in Mexico City than in the U.S., but we found similar emission ratios for most oxygenated VOCs and organic aerosol. Secondary formation of acetone may be more efficient in Mexico City than in the U.S., due to higher emissions of alkane precursors from the use of liquefied petroleum gas. Secondary formation of organic aerosol was similar between Mexico City and the U.S. Combining the data for all measured gas and aerosol species, we describe the budget of total observed organic carbon (TOOC), and find that the enhancement ratio of TOOC relative to CO is conserved between the early morning and mid afternoon despite large compositional changes. Finally, the influence of biomass burning is investigated using the measurements of acetonitrile, which was found to correlate with levoglucosan in the particle phase. Diurnal variations of acetonitrile indicate a contribution from local burning sources. Scatter plots of acetonitrile versus CO suggest that the contribution of biomass burning to the enhancement of most gas and aerosol species was not dominant and perhaps not dissimilar from observations in the U.S.
The zonal structure of tropical O3 and CO as observed by the Tropospheric Emission Spectrometer in November 2004 – Part 2: Impact of surface emissions on O3 and its precursors
Authors: Bowman K. W. , Jones D. B. A. , Logan J. A. , Worden H. , Boersma F. , Chang R. , Kulawik S. , Osterman G. , Hamer P. , Worden J.
Published: April 2010

Abstract. The impact of surface emissions on the zonal structure of tropical tropospheric ozone and carbon monoxide is investigated for November 2004 using satellite observations, in-situ measurements, and chemical transport models in conjunction with inverse-estimated surface emissions.Vertical ozone profiles from the Tropospheric Emission Spectrometer (TES) and ozone sonde measurements from the Southern Hemisphere Additional Ozonesondes (SHADOZ) network show elevated concentrations of ozone over Indonesia and Australia (60–70 ppb) in the lower troposphere against the backdrop of the well-known zonal "wave-one" pattern with ozone concentrations of (70–80 ppb) centered over the Atlantic . Observational evidence from TES CO vertical profiles and Ozone Monitoring Instrument (OMI) NO2 columns point to regional surface emissions as an important contributor to the elevated ozone over Indonesia. This contribution is investigated with the GEOS-Chem chemistry and transport model using surface emission estimates derived from an optimal inverse model, which was constrained by TES and Measurements Of Pollution In The Troposphere (MOPITT) CO profiles (Jones et al., 2009). These a posteriori estimates, which were over a factor of 2 greater than climatological emissions, reduced differences between GEOS-Chem and TES ozone observations by 30–40% over Indonesia. The response of the free tropospheric chemical state to the changes in these emissions is investigated for ozone, CO, NOx, and PAN. Model simulations indicate that ozone over Indonesian/Australian is sensitive to regional changes in surface emissions of NOx but relatively insensitive to lightning NOx. Over sub-equatorial Africa and South America, free tropospheric NOx was reduced in response to increased surface emissions potentially muting ozone production.
Variability and trends in stratospheric NO2 in Antarctic summer, and implications for stratospheric NOy
Authors: Cook P. A. , Roscoe H. K.
Published: April 2010

Abstract. NO2 measurements during 1990–2007, obtained from a zenith-sky spectrometer in the Antarctic, are analysed to determine the long-term changes in NO2. An atmospheric photochemical box model and a radiative transfer model are used to improve the accuracy of determination of the vertical columns from the slant column measurements, and to deduce the amount of NOy from NO2. We find that the NO2 and NOy columns in midsummer have large inter-annual variability superimposed on a broad maximum in 2000, with little or no overall trend over the full time period. These changes are robust to a variety of alternative settings when determining vertical columns from slant columns or determining NOy from NO2. They may signify similar changes in speed of the Brewer-Dobson circulation but with opposite sign, i.e. a broad minimum around 2000. Multiple regressions show significant correlation with solar and quasi-biennial-oscillation indices, and weak correlation with El Nino, but no significant overall trend, corresponding to an increase in Brewer-Dobson circulation of 1.4±3.5%/decade. There remains an unexplained cycle of amplitude and period at least 15% and 17 years, with minimum speed in about 2000.
On inferring isoprene emission surface flux from atmospheric boundary layer concentration measurements
Authors: Vilà-Guerau de Arellano J. , van den Dries K. , Pino D.
Published: April 2010

Abstract. We examine the dependence of the inferred isoprene surface emission flux from atmospheric concentration on the diurnal variability of the convective boundary layer (CBL). A series of systematic numerical experiments carried out using the mixed-layer technique enabled us to study the sensitivity of isoprene fluxes to the entrainment process, the partition of surface fluxes, the horizontal advection of warm/cold air masses and subsidence. Our findings demonstrate the key role played by the evolution of boundary layer height in modulating the retrieved isoprene flux. More specifically, inaccurate values of the potential temperature lapse rate lead to changes in the dilution capacity of the CBL and as a result the isoprene flux may be overestimated or underestimated by as much as 20%. The inferred emission flux estimated in the early morning hours is highly dependent on the accurate estimation of the discontinuity of the thermodynamic values between the residual layer and the rapidly forming CBL. Uncertainties associated with the partition of the sensible and latent heat flux also yield large deviations in the calculation of the isoprene surface flux. Similar results are obtained if we neglect the influence of warm or cold advection in the development of the CBL. We show that all the above-mentioned processes are non-linear, for which reason the dynamic and chemical evolutions of the CBL must be solved simultaneously. Based on the discussion of our results, we suggest the measurements needed to correctly apply the mixed-layer technique in order to minimize the uncertainties associated with the diurnal variability of the convective boundary layer.