bluuebunny/crossref_metadata_2025 huggingface dataset:
Interpretation of organic components from Positive Matrix Factorization of aerosol mass spectrometric data
Authors: Ulbrich I. M. , Canagaratna M. R. , Zhang Q. , Worsnop D. R. , Jimenez J. L.
Published: April 2010

Abstract. The organic aerosol (OA) dataset from an Aerodyne Aerosol Mass Spectrometer (Q-AMS) collected at the Pittsburgh Air Quality Study (PAQS) in September 2002 was analyzed with Positive Matrix Factorization (PMF). Three components – hydrocarbon-like organic aerosol OA (HOA), a highly-oxygenated OA (OOA-1) that correlates well with sulfate, and a less-oxygenated, semi-volatile OA (OOA-2) that correlates well with nitrate and chloride – are identified and interpreted as primary combustion emissions, aged SOA, and semivolatile, less aged SOA, respectively. The complexity of interpreting the PMF solutions of unit mass resolution (UMR) AMS data is illustrated by a detailed analysis of the solutions as a function of number of components and rotational forcing. A public web-based database of AMS spectra has been created to aid this type of analysis. Realistic synthetic data is also used to characterize the behavior of PMF for choosing the best number of factors, and evaluating the rotations of non-unique solutions. The ambient and synthetic data indicate that the variation of the PMF quality of fit parameter (Q, a normalized chi-squared metric) vs. number of factors in the solution is useful to identify the minimum number of factors, but more detailed analysis and interpretation are needed to choose the best number of factors. The maximum value of the rotational matrix is not useful for determining the best number of factors. In synthetic datasets, factors are "split" into two or more components when solving for more factors than were used in the input. Elements of the "splitting" behavior are observed in solutions of real datasets with several factors. Significant structure remains in the residual of the real dataset after physically-meaningful factors have been assigned and an unrealistic number of factors would be required to explain the remaining variance. This residual structure appears to be due to variability in the spectra of the components (especially OOA-2 in this case), which is likely to be a key limit of the retrievability of components from AMS datasets using PMF and similar methods that need to assume constant component mass spectra. Methods for characterizing and dealing with this variability are needed. Interpretation of PMF factors must be done carefully. Synthetic data indicate that PMF internal diagnostics and similarity to available source component spectra together are not sufficient for identifying factors. It is critical to use correlations between factor and external measurement time series and other criteria to support factor interpretations. True components with <5% of the mass are unlikely to be retrieved accurately. Results from this study may be useful for interpreting the PMF analysis of data from other aerosol mass spectrometers. Researchers are urged to analyze future datasets carefully, including synthetic analyses, and to evaluate whether the conclusions made here apply to their datasets.
Sensitivities of the absorptive partitioning model of secondary organic aerosol formation to the inclusion of water
Authors: Barley M. , Topping D. O. , Jenkin M. E. , McFiggans G.
Published: April 2010

Abstract. The predicted distribution of semi-volatile organic components between the gaseous and condensed phase as a function of ambient relative humidity and the specific form of the partitioning model used has been investigated. A mole fraction based model, modified so as not to use molar mass in the calculation, was found to predict identical RH dependence of component partitioning to that predicted by the conventional mass-based partitioning model which uses a molar mass averaged according to the number of moles in the condensed phase. A recently reported third version of the partitioning model using individual component molar masses was shown to give significantly different results to the other two models. Further sensitivities to an assumed pre-existing particulate loading and to parameterised organic component non-ideality are explored and shown to contribute significantly to the variation in predicted secondary organic particulate loading.
Aerosol dynamics simulations on the connection of sulphuric acid and new particle formation
Authors: Sihto S.-L. , Vuollekoski H. , Leppä J. , Riipinen I. , Kerminen V.-M. , Korhonen H. , Lehtinen K. E. J. , Boy M. , Kulmala M.
Published: April 2010

Abstract. We have performed a series of simulations with an aerosol dynamics box model to study the connection between new particle formation and sulphuric acid concentration. For nucleation either activation mechanism with a linear dependence on the sulphuric acid concentration, kinetic mechanism with a squared dependence on the sulphuric acid concentration or ternary H2O-H2SO4-NH3 nucleation was assumed. The aim was to study the factors that affect the sulphuric acid dependence during the early stages of particle growth, and specifically to find conditions which would yield the linear dependence between the particle number concentration at 3–6 nm and sulphuric acid, as observed in field experiments. The simulations showed that the correlation with sulphuric acid may change during the growth from nucleation size to 3–6 nm size range, the main reason being the size dependent growth rate between 1 and 3 nm. In addition, the assumed size for the nucleated clusters had a crucial impact on the sulphuric acid dependence at 3 nm. A linear dependence between the particle number concentration at 3 nm and sulphuric acid was achieved, when activation nucleation mechanism was used with a low saturation vapour pressure for the condensable organic vapour, or with nucleation taking place at ~2 nm instead of ~1 nm. Simulations with activation, kinetic and ternary nucleation showed that ternary nucleation reproduces too steep dependence on sulphuric acid as compared to the linear or square dependence observed in field measurements.
The potential contribution of organic salts to new particle growth
Authors: Barsanti K. C. , McMurry P. H. , Smith J. N.
Published: April 2010

Abstract. Field and lab measurements suggest that low-molecular weight (MW) organic acids and bases exist in accumulation and nucleation mode particles, despite their relatively high pure-liquid vapor pressures. The mechanism(s) by which such compounds contribute to the mass growth of existing aerosol particles and newly formed particles has not been thoroughly explored. One mechanism by which low-MW compounds may contribute to new particle growth is through the formation of organic salts. In this paper we use thermodynamic modeling to explore the potential for organic salt formation by atmospherically relevant organic acids and bases for two system types: one in which the relative contribution of ammonia vs. amines in forming organic salts was evaluated, the other in which the decrease in volatility of organic acids and bases due to organic salt formation was assessed. The modeling approach employed relied heavily on group contribution and other estimation methods for necessary physical and chemical parameters. The results of this work suggest that amines may be an important contributor to organic salt formation, and that experimental data are greatly needed to improve our understanding of organic salt formation in atmospherically relevant systems and to accurately predict the potential contribution of such salts to new particle growth.
Increased cloud activation potential of secondary organic aerosol for atmospheric mass loadings
Authors: King S. M. , Rosenoern T. , Shilling J. E. , Chen Q. , Martin S. T.
Published: April 2010

Abstract. The effect of organic particle mass loading from 1 to ≥100 μg m−3 on the cloud condensation nuclei (CCN) properties of mixed organic-sulfate particles was investigated in the Harvard Environmental Chamber. Mixed particles were produced by the condensation of organic molecules onto ammonium sulfate particles during the dark ozonolysis of α-pinene. A continuous-flow mode of the chamber provided stable conditions over long time periods, allowing for signal integration and hence increased measurement precision at low organic mass loadings representative of atmospheric conditions. CCN activity was measured at eight mass loadings for 80- and 100-nm particles grown on 50-nm sulfate seeds. A two-component (organic/sulfate) Köhler model, which included the particle heterogeneity arising from DMA size selection and from organic volume fraction for the selected 80- and 100-nm particles, was used to predict CCN activity. For organic mass loadings of 2.9 μg m−3 and greater, the observed activation curves were well predicted using a single set of physicochemical parameters for the organic component. For mass loadings of 1.74 μg m−3 and less, the observed CCN activity increased beyond predicted values using the same parameters, implying changed physicochemical properties of the organic component. A sensitivity analysis suggests that a drop in surface tension must be invoked to explain quantitatively the CCN observations at low SOA particle mass loadings. Other factors, such as decreased molecular weight, increased density, or increased van't Hoff factor, can contribute to the explanation but are quantitatively insufficient as the full explanation.
High formation of secondary organic aerosol from the photo-oxidation of toluene
Authors: Hildebrandt L. , Donahue N. M. , Pandis S. N.
Published: April 2010

Abstract. Toluene and other aromatics have long been viewed as the dominant anthropogenic secondary organic aerosol (SOA) precursors, but the SOA mass yields from toluene reported in previous studies vary widely. Experiments conducted in the Carnegie Mellon University environmental chamber to study SOA formation from the photo-oxidation of toluene show significantly larger SOA production than parameterizations employed in current air-quality models. Aerosol mass yields depend on experimental conditions: yields are higher under higher UV intensity, under low-NOx conditions and at lower temperatures. The extent of oxidation of the aerosol also varies with experimental conditions, consistent with ongoing, progressive photochemical aging of the toluene SOA. Measurements using a thermodenuder system suggest that the aerosol formed under high- and low-NOx conditions is semi-volatile. These results suggest that SOA formation from toluene depends strongly on ambient conditions. An approximate parameterization is proposed for use in air-quality models until a more thorough treatment accounting for the dynamic nature of this system becomes available.
Radicals in the marine boundary layer during NEAQS 2004: a model study of day-time and night-time sources and sinks
Authors: Sommariva R. , Osthoff H. D. , Brown S. S. , Bates T. S. , Baynard T. , Coffman D. , de Gouw J. A. , Goldan P. D. , Kuster W. C. , Lerner B. M. , Stark H. , Warneke C. , Williams E. J. , Fehsenfeld F. C. , Ravishankara A. R. , Trainer M.
Published: April 2010

Abstract. This paper describes a modelling study of several HOx and NOx species (OH, HO2, organic peroxy radicals, NO3 and N2O5) in the marine boundary layer. A model based upon the Master Chemical Mechanism (MCM) was constrained to observations of chemical and physical parameters made onboard the NOAA ship R/V Brown as part of the New England Air Quality Study (NEAQS) in the summer of 2004. The model was used to calculate [OH] and to determine the composition of the peroxy radical pool. Modelled [NO3] and [N2O5] were compared to in-situ measurements by Cavity Ring-Down Spectroscopy. The comparison showed that the model generally overestimated the measurements by 30–50%, on average. The model results were analyzed with respect to several chemical and physical parameters, including uptake of NO3 and N2O5 on fog droplets and on aerosol, dry deposition of NO3 and N2O5, gas-phase hydrolysis of N2O5 and reactions of NO3 with NMHCs and peroxy radicals. The results suggest that fog, when present, is an important sink for N2O5 via rapid heterogeneous uptake. The comparison between the model and the measurements were consistent with values of the heterogeneous uptake coefficient of N2O5 (γN2O5)>1×10−2, independent of aerosol composition in this marine environment. The analysis of the different loss processes of the nitrate radical showed the important role of the organic peroxy radicals, which accounted for a significant fraction (median: 15%) of NO3 gas-phase removal, particularly in the presence of high concentrations of dimethyl sulphide (DMS).
The impact of traffic emissions on atmospheric ozone and OH: results from QUANTIFY
Authors: Hoor P. , Borken-Kleefeld J. , Caro D. , Dessens O. , Endresen O. , Gauss M. , Grewe V. , Hauglustaine D. , Isaksen I. S. A. , Jöckel P. , Lelieveld J. , Myhre G. , Meijer E. , Olivie D. , Prather M. , Schnadt Poberaj C. , Shine K. P. , Staehelin J. , Tang Q. , van Aardenne J. , van Velthoven P. , Sausen R.
Published: April 2010

Abstract. To estimate the impact of emissions by road, aircraft and ship traffic on ozone and OH in the present-day atmosphere six different atmospheric chemistry models have been used. Based on newly developed global emission inventories for road, ship and aircraft emission data sets each model performed sensitivity simulations reducing the emissions of each transport sector by 5%. The model results indicate that on global annual average lower tropospheric ozone responds most sensitive to ship emissions (50.6%±10.9% of the total traffic induced perturbation), followed by road (36.7%±9.3%) and aircraft exhausts (12.7%±2.9%), respectively. In the northern upper troposphere between 200–300 hPa at 30–60° N the maximum impact from road and ship are 93% and 73% of the maximum effect of aircraft, respectively. The latter is 0.185 ppbv for ozone (for the 5% case) or 3.69 ppbv when scaling to 100%. On the global average the impact of road even dominates in the UTLS-region. The sensitivity of ozone formation per NOx molecule emitted is highest for aircraft exhausts. The local maximum effect of the summed traffic emissions on the ozone column predicted by the models is 0.2 DU and occurs over the northern subtropical Atlantic extending to central Europe. Below 800 hPa both ozone and OH respond most sensitively to ship emissions in the marine lower troposphere over the Atlantic. Based on the 5% perturbation the effect on ozone can exceed 0.6% close to the marine surface (global zonal mean) which is 80% of the total traffic induced ozone perturbation. In the southern hemisphere ship emissions contribute relatively strongly to the total ozone perturbation by 60%–80% throughout the year. Methane lifetime changes against OH are affected strongest by ship emissions up to 0.21 (± 0.05)%, followed by road (0.08 (±0.01)%) and air traffic (0.05 (± 0.02)%). Based on the full scale ozone and methane perturbations positive radiative forcings were calculated for road emissions (7.3±6.2 mWm−2) and for aviation (2.9±2.3 mWm−2). Ship induced methane lifetime changes dominate over the ozone forcing and therefore lead to a net negative forcing (−25.5±13.2 mWm−2).
The influence of traffic and wood combustion on the stable isotopic composition of carbon monoxide
Authors: Saurer M. , Prévôt A. S. H. , Dommen J. , Sandradewi J. , Baltensperger U. , Siegwolf R. T. W.
Published: April 2010

Abstract. Carbon monoxide in the atmosphere is originating from various combustion and oxidation processes. Recently, the proportion of CO resulting from the combustion of wood for domestic heating may have increased due to political measures promoting this renewable energy source. Here, we used the stable isotope composition of CO (δ13C and δ18O) for the characterization of different CO sources in Switzerland, along with other indicators for traffic and wood combustion (NOx-concentration, aerosol light absorption at different wavelengths). We assessed diurnal variations of the isotopic composition of CO at 3 sites during winter: a village site dominated by domestic heating, a site close to a motorway and a rural site. The isotope ratios of wood combustion emissions were studied at a test facility, indicating significantly lower δ18O of CO from wood combustion compared to traffic emissions. At the village and the motorway site, we observed very pronounced diurnal δ18O-variations of CO with an amplitude of up to 8‰. Solving the isotope mass balance equation for three distinct sources (wood combustion, traffic, clean background air) resulted in diurnal patterns consistent with other indicators for wood burning and traffic. The average night-time contribution of wood-burning to total CO was 70% at the village site, 49% at the motorway site and 29% at the rural site based on the isotope mass balance. The results, however, depend strongly on the pure source isotope values, which are not very well known. We therefore additionally applied a combined CO/NOx-isotope model for verification. Here, we separated the CO emissions into different sources based on distinct CO/NOx emissions ratios for wood combustion and traffic, and inserted this information in the isotope mass balance equation. Accordingly, a highly significant agreement between measured and calculated δ18O-values of CO was found (r=0.67, p<0.001). While different proxies for wood combustion all have their uncertainties, our results indicate that the oxygen isotope ratio of CO (but not the carbon isotope ratio) is an independent sensitive tool for source attribution studies.
Spatio-temporal variability and principal components of the particle number size distribution in an urban atmosphere
Authors: Costabile F. , Birmili W. , Klose S. , Tuch T. , Wehner B. , Wiedensohler A. , Franck U. , König K. , Sonntag A.
Published: April 2010

Abstract. A correct description of fine (diameter <1 μm) and ultrafine (<0.1 μm) aerosol particles in urban areas is of interest for particle exposure assessment but also basic atmospheric research. We examined the spatio-temporal variability of atmospheric aerosol particles (size range 3–800 nm) using concurrent number size distribution measurements at a maximum of eight observation sites in and around Leipzig, a city in Central Europe. Two main experiments were conducted with different time span and number of observation sites (2 years at 3 sites; 1 month at 8 sites). A general observation was that the particle number size distribution varied in time and space in a complex fashion as a result of interaction between local and far-range sources, and the meteorological conditions. To identify statistically independent factors in the urban aerosol, different runs of principal component (PC) analysis were conducted encompassing aerosol, gas phase, and meteorological parameters from the multiple sites. Several of the resulting PCs, outstanding with respect to their temporal persistence and spatial coverage, could be associated with aerosol particle modes: a first accumulation mode ("droplet mode", 300–800 nm), considered to be the result of liquid phase processes and far-range transport; a second accumulation mode (centered around diameters 90–250 nm), considered to result from primary emissions as well as aging through condensation and coagulation; an Aitken mode (30–200 nm) linked to urban traffic emissions in addition to an urban and a rural Aitken mode; a nucleation mode (5–20 nm) linked to urban traffic emissions; nucleation modes (3–20 nm) linked to photochemically induced particle formation; an aged nucleation mode (10–50 nm). Additional PCs represented only local sources at a single site, or infrequent phenomena. In summary, the analysis of size distributions of high time and size resolution yielded a surprising wealth of statistical aerosol components occurring in the urban atmosphere over one single city. A paradigm on the behaviour of sub-μm urban aerosol particles is proposed, with recommendations how to efficiently monitor individual sub-fractions across an entire city.
Distribution of VOCs between air and snow at the Jungfraujoch high alpine research station, Switzerland, during CLACE 5 (winter 2006)
Authors: Starokozhev E. , Fries E. , Cycura A. , Püttmann W.
Published: April 2010

Abstract. Volatile organic compounds (VOCs) were analyzed in air and snow samples at the Jungfraujoch high alpine research station in Switzerland as part of CLACE 5 (CLoud and Aerosol Characterization Experiment) during February/March 2006. The fluxes of individual compounds in ambient air were calculated from gas phase concentrations and wind speed. The highest concentrations and flux values were observed for the aromatic hydrocarbons benzene (14.3 μg.m−2 s−1), 1,3,5-trimethylbenzene (5.27 μg.m−2 s−1), toluene (4.40 μg.m−2 −1), and the aliphatic hydrocarbons i-butane (7.87 μg.m−2 s−1), i-pentane (3.61 μg.m−2 s−1) and n-butane (3.23 μg.m−2 s−1). The measured concentrations and fluxes were used to calculate the efficiency of removal of VOCs by snow, which is defined as difference between the initial and final concentration/flux values of compounds before and after wet deposition. The removal efficiency was calculated at −24°C (−13.7°C) and ranged from 37% (35%) for o-xylene to 93% (63%) for i-pentane. The distribution coefficients of VOCs between the air and snow phases were derived from published poly-parameter linear free energy relationship (pp-LFER) data, and compared with distribution coefficients obtained from the simultaneous measurements of VOC concentrations in air and snow at Jungfraujoch. The coefficients calculated from pp-LFER exceeded those values measured in the present study, which indicates more efficient snow scavenging of the VOCs investigated than suggested by theoretical predictions.
Contrasting atmospheric boundary layer chemistry of methylhydroperoxide (CH3OOH) and hydrogen peroxide (H2O2) above polar snow
Authors: Frey M. M. , Hutterli M. A. , Chen G. , Sjostedt S. J. , Burkhart J. F. , Friel D. K. , Bales R. C.
Published: April 2010

Abstract. Atmospheric hydroperoxides (ROOH) were measured at Summit, Greenland (72.97° N, 38.77° W) in summer 2003 (SUM03) and spring 2004 (SUM04) and South Pole in December 2003 (SP03). The two dominant hydroperoxides were H2O2 and CH3OOH (from here on MHP) with average (±1σ) mixing ratios of 1448 (±688) pptv, 204 (±162) and 278 (±67) for H2O2 and 578 (±377) pptv, 139 (±101) pptv and 138 (±89) pptv for MHP, respectively. In early spring, MHP dominated the ROOH budget and showed night time maxima and daytime minima, out of phase with the diurnal cycle of H2O2, suggesting that the organic peroxide is controlled by photochemistry, while H2O2 is largely influenced by temperature driven exchange between the atmosphere and snow. Highly constrained photochemical box model runs yielded median ratios between modeled and observed MHP of 52%, 148% and 3% for SUM03, SUM04 and SP03, respectively. At Summit firn air measurements and model calculations suggest a daytime sink of MHP in the upper snow pack, which decreases in strength through the spring season into the summer. Up to 50% of the estimated sink rates of 1–5×1011 molecules m−3 s−1 equivalent to 24–96 pptv h−1 can be explained by photolysis and reaction with the OH radical in firn air and in the quasi-liquid layer on snow grains. Rapid processing of MHP in surface snow is expected to contribute significantly to a photochemical snow pack source of formaldehyde (CH2O). Conversely, summer levels of MHP at South Pole are inconsistent with the prevailing high NO concentrations, and cannot be explained currently by known photochemical precursors or transport, thus suggesting a missing source. Simultaneous measurements of H2O2, MHP and CH2O allow to constrain the NO background today and potentially also in the past using ice cores, although it seems less likely that MHP is preserved in firn and ice.
Open ocean DMS air/sea fluxes over the eastern South Pacific Ocean
Authors: Marandino C. A. , De Bruyn W. J. , Miller S. D. , Saltzman E. S.
Published: April 2010

Abstract. Air/sea fluxes of dimethylsulfide (DMS) were measured by eddy correlation over the Eastern South Pacific Ocean during January 2006. The cruise track extended from Manzanillo, Mexico, along 110° W, to Punta Arenas, Chile. Bulk air and surface ocean DMS levels were also measured and gas transfer coefficients (kDMS) were computed. Air and seawater DMS measurements were made using chemical ionization mass spectrometry (API-CIMS) and a gas/liquid membrane equilibrator. Mean surface seawater DMS concentrations were 3.8±2.2 nM and atmospheric mixing ratios were 340±370 ppt. The air/sea flux of DMS was uniformly out of the ocean, with an average value of 12±15 μmol m−2 d−1. Sea surface concentration and flux were highest around 15° S, in a region influenced by shelf waters and lowest around 25° S, in low chlorophyll gyre waters. The DMS gas transfer coefficient exhibited a linear wind speed-dependence over the wind speed range of 1 to 9 m s−1. This relationship is compared with previously measured estimates of k from DMS, CO2, and dual tracer data from the Atlantic and Pacific Ocean, and with the NOAA/COARE gas transfer model. The model generated slope of k vs. wind speed is at the low end of those observed in previous DMS field studies.
Reactive nitrogen in Mexico City and its relation to ozone-precursor sensitivity: results from photochemical models
Authors: Sillman S. , West J. J.
Published: April 2010

Abstract. We use results of a 3-D photochemistry/transport model for ozone formation in Mexico City during events in 1997 to investigate ambient concentrations of reactive nitrogen in relation to ozone-precursor sensitivity. Previous results from other locations suggest that ratios such as O3/NOy and H2O2/HNO3 might provide measurement-based indicators for NOx-sensitive or VOC-sensitive conditions. Mexico City presents a different environment due to its high concentrations of VOC and high level of pollutants in general. The model predicts a correlation between PAN and O3 with relatively high PAN/O3 (0.07), which is still lower than measured values. The model PAN is comparable with results from a model for Paris but much higher than were found in Nashville in both models and measurements. The difference is due in part to the lower temperature in Mexico City relative to Nashville. Model HNO3 in Mexico City is unusually low for an urban area and PAN/HNO3 is very high, probably due to the high ratio of reactivity-weighted VOC to NOx. The model predicts that VOC-sensitive chemistry in Mexico is associated with high NOx, NOy and NOx/NOy and with low O3/NOy and H2O2/HNO3, suggesting that these indicators work well for Mexico City. The relation between ozone-precursor sensitivity and either O3/NOz or O3/HNO3 is more ambiguous. VOC-sensitive conditions are associated with higher O3/HNO3 than would be found in NOx-sensitive conditions, but model O3/HNO3 associated with both NOx-sensitive and VOC-sensitive chemistry is higher in Mexico than in other cities. The model predicts a mixed pattern of ozone-precursor sensitivity in Mexico City, with VOC-sensitive conditions in the morning and NOx-sensitive in the afternoon, in contrast to results from other models for more recent events that predicted strongly VOC- sensitive conditions throughout the day. The difference in predicted ozone-precursor sensitivity is most likely due to different emission rates and to changes in emissions over time. The model with mixed sensitivity predicts much lower ambient NOx and NOx/NOy than the strongly VOC-sensitive model.
Evidence for Asian dust effects from aerosol plume measurements during INTEX-B 2006 near Whistler, BC
Authors: Leaitch W. R. , Macdonald A. M. , Anlauf K. G. , Liu P. S. K. , Toom-Sauntry D. , Li S.-M. , Liggio J. , Hayden K. , Wasey M. A. , Russell L. M. , Takahama S. , Liu S. , van Donkelaar A. , Duck T. , Martin R. V. , Zhang Q. , Sun Y. , McKendry I. , Shantz N. C. , Cubison M.
Published: April 2010

Abstract. Several cases of aerosol plumes resulting from trans-Pacific transport were observed between 2 km and 5.3 km at Whistler, BC from 22 April 2006 to 15 May 2006. The fine particle (<1 μm) chemical composition of most of the plumes was dominated by sulphate that ranged from 1–5 μg m−3 as measured with a Quadrapole Aerosol Mass Spectrometer (Q-AMS). Coarse particles (>1 μm) were enhanced in all sulphate plumes. Fine particle organic mass concentrations were relatively low in most plumes and were nominally anti-correlated with the increases in the number concentrations of coarse particles. The ion chemistry of coarse particles sampled at Whistler Peak was dominated by calcium, sodium, nitrate, sulphate and formate. Scanning transmission X-ray microscopy of coarse particles sampled from the NCAR C-130 aircraft relatively close to Whistler indicated carbonate, potassium and organic functional groups, in particular the carboxyl group. Asian plumes reaching Whistler, BC during the INTEX-B study were not only significantly reduced of fine particle organic material, but organic compounds were attached to coarse particles in significant quantities. Suspension of dust with deposited organic material and scavenging of organic materials by dust near anthropogenic sources are suggested, and if any secondary organic aerosol (SOA) was formed during transport from Asian source regions across the Pacific it was principally associated with the coarse particles. An average of profiles indicates that trans-Pacific transport between 2 and 5 km during this period increased ozone by about 10 ppbv and fine particle sulphate by 0.2–0.5 μg m−3. The mean sizes of the fine particles in the sulphate plumes were larger when dust particles were present and smaller when the fine particle organic mass concentration was larger and dust was absent. The coarse particles of dust act to accumulate sulphate, nitrate and organic material in larger particles, diminishing the role of these compounds in indirect radiative forcing, but potentially enhancing their roles in direct radiative forcing.
The zonal structure of tropical O3 and CO as observed by the Tropospheric Emission Spectrometer in November 2004 – Part 1: Inverse modeling of CO emissions
Authors: Jones D. B. A. , Bowman K. W. , Logan J. A. , Heald C. L. , Liu J. , Luo M. , Worden J. , Drummond J.
Published: April 2010

Abstract. We conduct an inverse modeling analysis of measurements of atmospheric CO from the TES and MOPITT satellite instruments using the GEOS-Chem global chemical transport model to quantify emissions of CO in the tropics in November 2004. We also assess the consistency of the information provided by TES and MOPITT on surface emissions of CO. We focus on the tropics in November 2004, during the biomass burning season, because TES observations of CO and O3 and MOPITT observations of CO reveal significantly greater abundances of these gases than simulated by the GEOS-Chem model during that period. We find that both datasets suggest substantially greater emissions of CO from sub-equatorial Africa and the Indonesian/Australian region than in the climatological emissions in the model. The a posteriori emissions from sub-equatorial Africa based on TES and MOPITT data were 173 Tg CO/yr and 184 Tg CO/yr, respectively, compared to the a priori of 95 Tg CO/yr. In the Indonesian/Australian region, the a posteriori emissions inferred from TES and MOPITT data were 155 Tg CO/yr and 185 Tg CO/yr, respectively, whereas the a priori was 69 Tg CO/yr. The differences between the a posteriori emission estimates obtained from the two datasets are generally less than 20%. The a posteriori emissions significantly improve the simulated distribution of CO, however, large regional residuals remain, and are likely due to systematic errors in the analysis. Reducing these residuals and improving the accuracy of top-down emission estimates will require better characterization of systematic errors in the observations and the model (chemistry and transport).
Global emissions of non-methane hydrocarbons deduced from SCIAMACHY formaldehyde columns through 2003–2006
Authors: Stavrakou T. , Müller J.-F. , De Smedt I. , Van Roozendael M. , van der Werf G. R. , Giglio L. , Guenther A.
Published: April 2010

Abstract. Formaldehyde columns retrieved from the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography/Chemistry (SCIAMACHY) instrument onboard ENVISAT satellite through 2003 to 2006 are used as top-down constraints to derive updated global biogenic and biomass burning flux estimates for the non-methane volatile organic compounds (NMVOCs) precursors of formaldehyde. Our interest is centered over regions experiencing strong emissions, and hence exhibiting a high signal-to-noise ratio and lower measurement uncertainties. The formaldehyde dataset used in this study has been recently made available to the community and complements the long record of formaldehyde measurements from the Global Ozone Monitoring Experiment (GOME). We use the IMAGESv2 global chemistry-transport model driven by the Global Fire Emissions Database (GFED) version 1 or 2 for biomass burning, and from the newly developed MEGAN-ECMWF isoprene emission database. The adjoint of the model is implemented in a grid-based framework within which emission fluxes are derived at the model resolution, together with a differentiation of the sources in a grid cell. Two inversion studies are conducted using either the GFEDv1 or GFEDv2 as a priori for the pyrogenic fluxes. Although on the global scale the inferred emissions from the two categories exhibit only weak deviations from the corresponding a priori estimates, the regional updates often present large departures from their a priori values. The posterior isoprene emissions over North America, amounting to about 34 Tg C/yr, are estimated to be on average by 25% lower than the a priori over 2003–2006, whereas a strong increase (55%) is deduced over the south African continent, the optimized emission being estimated at 57 Tg C/yr. Over Indonesia the biogenic emissions appear to be overestimated by 20–30%, whereas over Indochina and the Amazon basin during the wet season the a priori inventory captures both the seasonality and the magnitude of the observed columns. Although neither biomass burning inventory seems to be consistent with the data over all regions, pyrogenic estimates inferred from the two inversions are reasonably similar, despite their a priori deviations. A number of sensitivity experiments are conducted in order to assess the impact of uncertainties related to the inversion setup and the chemical mechanism. Whereas changes in the background error covariance matrix have only a limited impact on the posterior fluxes, the use of an alternative isoprene mechanism characterized by lower HCHO yields (the GEOS-Chem mechanism) increases the posterior isoprene source estimate by 11% over northern America, and by up to 40% in tropical regions.
Reactive oxidation products promote secondary organic aerosol formation from green leaf volatiles
Authors: Hamilton J. F. , Lewis A. C. , Carey T. J. , Wenger J. C. , Borrás i Garcia E. , Muñoz A.
Published: April 2010

Abstract. Green leaf volatiles (GLVs) are an important group of chemicals released by vegetation which have emission fluxes that can be significantly increased when plants are damaged or stressed. A series of simulation chamber experiments has been conducted at the European Photoreactor in Valencia, Spain, to investigate secondary organic aerosol (SOA) formation from the atmospheric oxidation of the major GLVs cis-3-hexenylacetate and cis-3-hexen-1-ol. Liquid chromatography-ion trap mass spectrometry was used to identify chemical species present in the SOA. Cis-3-hexen-1-ol proved to be a more efficient SOA precursor due to the high reactivity of its first generation oxidation product, 3-hydroxypropanal, which can hydrate and undergo further reactions with other aldehydes resulting in SOA dominated by higher molecular weight oligomers. The lower SOA yields produced from cis-3-hexenylacetate are attributed to the acetate functionality, which inhibits oligomer formation in the particle phase. Based on observed SOA yields and best estimates of global emissions, these compounds may be calculated to be a substantial unidentified global source of SOA, contributing 1–5 TgC yr−1, equivalent to around a third of that predicted from isoprene. Molecular characterization of the SOA, combined with organic mechanistic information, has provided evidence that the formation of organic aerosols from GLVs is closely related to the reactivity of their first generation atmospheric oxidation products, and indicates that this may be a simple parameter that could be used in assessing the aerosol formation potential for other unstudied organic compounds in the atmosphere.
Photodegradation of secondary organic aerosol generated from limonene oxidation by ozone studied with chemical ionization mass spectrometry
Authors: Pan X. , Underwood J. S. , Xing J.-H. , Mang S. A. , Nizkorodov S. A.
Published: April 2010

Abstract. Photodegradation of secondary organic aerosol (SOA) prepared by ozone-initiated oxidation of D-limonene is studied with an action spectroscopy approach, which relies on detection of volatile photoproducts with chemical ionization mass-spectrometry as a function of the UV irradiation wavelength. Efficient photodegradation is observed for a broad range of ozone (0.1–300 ppm) and D-limonene (0.02–3 ppm) concentrations used in the preparation of SOA. The observed photoproducts are dominated by oxygenated C1-C3 compounds such as methanol, formic acid, acetaldehyde, acetic acid, and acetone. The irradiation wavelength dependence of the combined yield of the photoproducts closely tracks the absorption spectrum of the SOA material suggesting that photodegradation is not limited to the UV wavelengths. Kinetic simulations suggest that RO2+HO2/RO2 reactions represent the dominant route to photochemically active carbonyl and peroxide species in the limonene SOA prepared in these experiments. Similar photodegradation processes are likely to occur in realistic SOA produced by OH- or O3-initiated oxidation of biogenic volatile organic compounds in clean air.
Particulate absorption of solar radiation: anthropogenic aerosols vs. dust
Authors: Wang C. , Jeong G. R. , Mahowald N.
Published: April 2010

Abstract. Particulate solar absorption is a critical factor in determining the value and even sign of the direct radiative forcing of aerosols. The heating to the atmosphere and cooling to the Earth's surface caused by this absorption are hypothesized to have significant climate impacts. We find that anthropogenic aerosols play an important role around the globe in total particulate absorption of solar radiation. The global-average anthropogenic fraction in total aerosol absorbing optical depth exceeds 65% in all seasons. Combining the potentially highest dust absorption with the lowest anthropogenic absorption within our model range, this fraction would still exceed 47% in most seasons except for boreal spring (36%) when dust abundance reaches its peak. Nevertheless, dust aerosol is still a critical absorbing constituent over places including North Africa, the entire tropical Atlantic, and during boreal spring in most part of Eurasian continent. The equality in absorbing solar radiation of dust and anthropogenic aerosols appears to be particularly important over Indian subcontinent and nearby regions as well as North Africa.
Equatorial total column of nitrous oxide as measured by IASI on MetOp-A: implications for transport processes
Authors: Ricaud P. , Attié J.-L. , Teyssèdre H. , El Amraoui L. , Peuch V.-H. , Matricardi M. , Schluessel P.
Published: April 2010

Abstract. In this paper we use the total columns of nitrous oxide (N2O) as retrieved from the radiance spectra as measured by the Infrared Atmospheric Sounding Interferometer (IASI) instrument aboard the MetOp-A platform and distributed by the European Organisation for the Exploitation of Meteorological Satellites (EUMETSAT) during the March–May (MAM) 2008 period. Since the total column of N2O reflects concentrations in the middle troposphere, cloud-free columnar N2O measurements are used to assess transport processes in the equatorial band (10° S–10° N). We compare the measured data set with the outputs produced by the 3-D chemical-transport model MOCAGE during the period MAM 2002–2004. To reflect MAM 2008 concentrations, MOCAGE results have been scaled by a factor 1.0125 in order to represent the change in concentration of N2O since 2004. IASI N2O equatorial measurements show a maximum over Africa (4.96×10−3 kg m−2) and a minimum over South America (4.86×10−3 kg m−2) in reasonable agreement with the outputs from MOCAGE despite the fact that emissions of N2O are more intense over America than over Africa. The amplitude of the longitudinal variation of total column N2O along the equatorial band is twice as intense in the measurements (~1.6%) than as in the model calculations (~0.8%), and much greater than the IASI mean random error (0.16–0.33%). A difference between the two data sets is observed above the Western Pacific (110° E–150° E) with a marked minimum in IASI compared to MOCAGE. Recent theoretical studies (Ricaud et al., 2007 and 2009) have shown the potentially important effect of the Walker and the Hadley cells on the tropospheric distribution of N2O in producing a local maximum in N2O above Africa. Based on equatorial total columns of N2O retrieved from IASI, our results are consistent with the fact that Africa is a zone of convergence of airmasses coming from different convective regions whilst Western Pacific behaves more like a divergence zone.
Wave fluxes of equatorial Kelvin waves and QBO zonal wind forcing derived from SABER and ECMWF temperature space-time spectra
Authors: Ern M. , Preusse P.
Published: April 2010

Abstract. The quasi-biennial oscillation (QBO) of the zonal mean zonal wind is a dynamical phenomenon of the tropical middle atmosphere. Influences of the QBO can even be found at mid and high latitudes. It is widely accepted that the phase descent of alternating tropical easterlies and westerlies is driven by atmospheric waves of both global scale (equatorial wave modes like Kelvin, equatorial Rossby, Rossby-gravity, or inertia-gravity waves), as well as mesoscale gravity waves. However, the relative distribution of the different types of waves to the forcing of the QBO winds is highly uncertain. This is the case because until recently there were no high resolution long-term global measurements in the stratosphere. In our study we estimate Kelvin wave momentum flux and the contribution of zonal wind forcing by Kelvin waves based on space-time spectra determined from both Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) temperature measurements as well as temperatures from European Centre for Medium-Range Weather Forecasts (ECMWF) operational analyses. Peak values of total Kelvin wave zonal wind forcing found are about 0.2 m/s/day. There is good agreement between SABER and ECMWF results. Altitude-time cross sections are shown and the results are compared to the total wave forcing required to balance the background atmosphere. Sometimes Kelvin wave forcing is sufficient to explain almost the whole total wave forcing required for the momentum balance during the transition from QBO easterly to westerly winds. This is especially the case during the periods of strong westerly wind shear when the zonal wind is between −20 and 10 m/s at the equator in the altitude range 20 to 35 km. During other parts of the phases of strong westerly wind shear, however, the contribution of Kelvin waves can be comparably low and the missing wave forcing, which is often attributed to mesoscale gravity waves or intermediate scale waves, can be the by far dominant contribution of the QBO forcing. It is also found that seasonal variations of Kelvin wave accelerations could play an important role for the maintenance of the QBO westerly wind jets in the lower stratosphere.
Ammonia in positively charged pre-nucleation clusters: a quantum-chemical study and atmospheric implications
Authors: Nadykto A. B. , Yu F. , Herb J.
Published: April 2010

Abstract. The quantum-chemical treatment of pre-nucleation clusters consisting of atmospheric nucleation precursors is critically important for the understanding of the molecular nature of atmospheric nucleation. In the present study, the influence of ammonia on the thermochemical stability of positively charged pre-nucleation clusters has been studied using the Density Functional Theory (DFT). The formation of binary (NH4+)(H2O)n and ternary (NH4+)(H2SO4)(H2O)n ionic clusters and the conversion of (H3O+)(H2O)n−1 into (NH4+)(H2O)n and (H3O+) (H2SO4)(H2O)n−1 into (NH4+)(H2SO4)(H2O)n have been investigated. The thermochemical analysis carried out in the present study shows both (H3O+)(H2O)n−1→(NH4+) (H2O)n and (H2SO4)(H3O+)(H2O)n−1→(NH4+)(H2SO4) (H2O)n transformations to be favorable thermodynamically and gives us a clear indication of the important role of ammonia in the conversion of positively charged clusters containing hydronium (H3O+) into those containing protonated ammonia. Under typical continental boundary layer condition, a large fraction of small positive ions may contain ammonia, but most of neutral and negative hydrated sulfuric acid monomers do not contain ammonia. In term of absolute concentrations, around 1000 cm−3 out of 107 cm−3 of sulfuric acid momoners contain ammonia. (NH4)+(H2O)n clusters appear to dominate the concentrations of small positive ions. Because of the weak affinity of sulfuric acid molecules to (H3O+)(H2O)n and (NH4+)(H2O)n ions (n≤6), the concentrations of both ammoniated and un-ammoniated sulfuric acid water proton clusters are quite low. The atmospheric implications of the obtained results are discussed.
Charged and total particle formation and growth rates during EUCAARI 2007 campaign in Hyytiälä
Authors: Manninen H. E. , Nieminen T. , Riipinen I. , Yli-Juuti T. , Gagné S. , Asmi E. , Aalto P. P. , Petäjä T. , Kerminen V.-M. , Kulmala M.
Published: April 2010

Abstract. Despite the fact that frequent aerosol formation has been observed in various locations in the atmosphere, the overall magnitude of the new particle formation as a particle source is still unclear. In order to understand the particle formation and growth processes, we investigate the magnitudes of the particle formation and growth rates at the size where the real atmospheric nucleation and activation occurs. The relative contribution of neutral and charged particles to the new particle formation rate is also studied. The data include particle and ion number size distributions and total particle concentration measurements at a boreal forest site in Hyytiälä, Finland, during the spring 2007 EUCAARI field campaign. The total and charged particle formation rates differed from each other by approximately an order of magnitude. The median formation rates of 2 nm total and charged particles were 0.65 cm−3 s−1 and 0.03 cm−3 s−1, respectively. The median growth rates of particles in size classes 1.3–3, 3–7 and 7–20 nm were 1.9, 3.6 and 4.2 nm h−1, respectively. The calculated ion-ion recombination rates were about the same order of magnitude as the ion-induced formation rates. The results indicate that the ion-induced nucleation involving the ion-ion recombination products, i.e. ion mediated nucleation, contributes approximately 10% to the boreal forest new particle formation events.