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Atmospheric Chemistry and Physics - Current Research Articles



Current research articles: Atmospheric Chemistry

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Atmospheric Chemistry and Physics - published by Copernicus Publications

ACP is an international scientific open access journal dedicated to the publication and public discussion of high quality studies investigating the Earth's atmosphere and the underlying chemical and physical processes. It covers the altitude range from the land and ocean surface up to the turbopause, including the troposphere, stratosphere and mesosphere.




Current articles of the journal:



Atmospheric oxidation of 1,3-butadiene: characterization of gas and aerosol reaction products and implications for PM2.5

Atmospheric oxidation of 1,3-butadiene: characterization of gas and aerosol reaction products and implications for PM2.5

Atmospheric Chemistry and Physics, 14, 13681-13704, 2014

Author(s): M. Jaoui, M. Lewandowski, K. Docherty, J. H. Offenberg, and T. E. Kleindienst

Secondary organic aerosol (SOA) was generated by irradiating 1,3-butadiene (13BD) in the presence of H2O2 or NOx. Experiments were conducted in a smog chamber operated in either flow or batch mode. A filter/denuder sampling system was used for simultaneously collecting gas- and particle-phase products. The chemical composition of the gas phase and SOA was analyzed using derivative-based methods (BSTFA, BSTFA + PFBHA, or DNPH) followed by gas chromatography–mass spectrometry (GC–MS) or high-performance liquid chromatography (HPLC) analysis of the derivative compounds. The analysis showed the occurrence of more than 60 oxygenated organic compounds in the gas and particle phases, of which 31 organic monomers were tentatively identified. The major identified products include glyceric acid, d-threitol, erythritol, d-threonic acid, meso-threonic acid, erythrose, malic acid, tartaric acid, and carbonyls including glycolaldehyde, glyoxal, acrolein, malonaldehyde, glyceraldehyde, and peroxyacryloyl nitrate (APAN). Some of these were detected in ambient PM2.5 samples, and could potentially serve as organic markers of 13BD. Furthermore, a series of oligoesters were detected and found to be produced through chemical reactions occurring in the aerosol phase between compounds bearing alcoholic groups and compounds bearing acidic groups. SOA was analyzed for organic mass to organic carbon (OM /OC) ratio, effective enthalpy of vaporization (Δ Hvapeff), and aerosol yield. The average OM /OC ratio and SOA density were 2.7 ± 0.09 and 1.2 ± 0.05, respectively. The average Δ Hvapeff was ?26.08 ± 1.46 kJ mol?1, a value lower than that of isoprene SOA. The average laboratory SOA yield measured in this study at aerosol mass concentrations between 22.5 and 140.2 ?g m?3 was 0.025 ± 0.011, a value consistent with the literature (0.021–0.178). While the focus of this study has been examination of the particle-phase measurements, the gas-phase photooxidation products have also been examined.

The contribution of SOA products from 13BD oxidation to ambient PM2.5 was investigated by analyzing a series of ambient PM2.5 samples collected in several locations around the United States. In addition to the occurrence of several organic compounds in field and laboratory samples, glyceric acid, d-threitol, erythritol, erythrose, and threonic acid were found to originate only from the oxidation of 13BD based on our previous experiments involving chamber oxidation of a series of hydrocarbons. Initial attempts have been made to quantify the concentrations of these compounds. The average concentrations of these compounds in ambient PM2.5 samples from the California Research at the Nexus of Air Quality and Climate Change (CalNex) study ranged from 0 to approximately 14.1 ng m?3. The occurrence of several other compounds in both laboratory and field samples suggests that SOA originating from 13BD oxidation could contribute to the ambient aerosol mainly in areas with high 13BD emission rates.

Posted on 20 December 2014 | 12:00 am


The contribution of plume-scale nucleation to global and regional aerosol and CCN concentrations: evaluation and sensitivity to emissions changes

The contribution of plume-scale nucleation to global and regional aerosol and CCN concentrations: evaluation and sensitivity to emissions changes

Atmospheric Chemistry and Physics, 14, 13661-13679, 2014

Author(s): R. G. Stevens and J. R. Pierce

We implement the Predicting Particles Produced in Power-Plant Plumes (P6) sub-grid sulphate parameterization for the first time into a global chemical-transport model with online aerosol microphysics, the GEOS-Chem-TOMAS model. Compared to simulations using two other previous treatments of sub-grid sulphate, simulations using P6 sub-grid sulphate predicted similar or smaller increases (depending on other model assumptions) in globally, annually averaged concentrations of particles larger than 80 nm (N80). We test in simulations using P6 sub-grid sulphate the sensitivity of particle number concentrations to changes in SO2 or NOx emissions to represent recent emissions control changes. For global increases of 50% in emissions of either SO2 or NOx, or both SO2 and NOx, we find that globally, annually averaged N80 increase by 9.00, 1.47, or 10.24% respectively. However, both sub-grid and grid-resolved processes contribute to these changes. Finally, we compare the model results against observations of particle number concentrations. Compared with previous treatments of sub-grid sulphate, use of the P6 parameterization generally improves correlation with observed particle number concentrations. The P6 parameterization is able to resolve spatial heterogeneity in new-particle formation and growth that cannot be resolved by any constant assumptions about sub-grid sulphate. However, the differences in annually averaged aerosol size distributions due to the treatment of sub-grid sulphate at the measurement sites examined here are too small to unambiguously establish P6 as providing better agreement with observations.

Posted on 20 December 2014 | 12:00 am


Biotic stress: a significant contributor to organic aerosol in Europe?

Biotic stress: a significant contributor to organic aerosol in Europe?

Atmospheric Chemistry and Physics, 14, 13643-13660, 2014

Author(s): R. Bergström, M. Hallquist, D. Simpson, J. Wildt, and T. F. Mentel

We have investigated the potential impact on organic aerosol formation from biotic stress-induced emissions (SIE) of organic molecules from forests in Europe (north of lat. 45° N). Emission estimates for sesquiterpenes (SQT), methyl salicylate (MeSA) and unsaturated C17 compounds, due to different stressors, are based on experiments in the Jülich Plant Atmosphere Chamber (JPAC), combined with estimates of the fraction of stressed trees in Europe based on reported observed tree damage.

SIE were introduced in the EMEP MSC-W chemical transport model and secondary organic aerosol (SOA) yields from the SIE were taken from the JPAC experiments. Based on estimates of current levels of infestation and the JPAC aerosol yields, the model results suggest that the contribution to SOA in large parts of Europe may be substantial. It is possible that SIE contributes as much, or more, to organic aerosol than the constitutive biogenic VOC emissions, at least during some periods. Based on the assumptions in this study, SIE-SOA are estimated to constitute between 50 and 70 % of the total biogenic SOA (BSOA) in a current-situation scenario where the biotic stress in northern and central European forests causes large SIE of MeSA and SQT. An alternative current-situation scenario with lower SIE, consisting solely of SQT, leads to lower SIE-SOA, between 20 and 40 % of the total BSOA.

Hypothetical future scenarios with increased SIE, due to higher degrees of biotic stress, show that SOA formation due to SIE can become even larger.

Unsaturated C17 BVOC (biogenic volatile organic compounds) emitted by spruce infested by the forest-honey generating bark louse, Cinara pilicornis, have a high SOA-forming potential. A model scenario investigating the effect of a regional, episodic infestation of Cinara pilicornis in Baden-Württemberg, corresponding to a year with high production of forest honey, shows that these types of events could lead to very large organic aerosol formation in the infested region.

We have used the best available laboratory data on biotic SIE applicable to northern and central European forests. Using these data and associated assumptions, we have shown that SIE are potentially important for SOA formation but the magnitude of the impact is uncertain and needs to be constrained by further laboratory, field and modelling studies. As an example, the MeSA, which is released as a consequence of various types of biotic stress, is found to have a potentially large impact on SIE-SOA in Europe, but different assumptions regarding the nighttime chemistry of MeSA can change its SOA potential substantially. Thus, further investigations of the atmospheric chemistry of MeSA and observational field studies are needed to clarify the role of this compound in the atmosphere.

Posted on 20 December 2014 | 12:00 am


A physically based framework for modeling the organic fractionation of sea spray aerosol from bubble film Langmuir equilibria

A physically based framework for modeling the organic fractionation of sea spray aerosol from bubble film Langmuir equilibria

Atmospheric Chemistry and Physics, 14, 13601-13629, 2014

Author(s): S. M. Burrows, O. Ogunro, A. A. Frossard, L. M. Russell, P. J. Rasch, and S. M. Elliott

The presence of a large fraction of organic matter in primary sea spray aerosol (SSA) can strongly affect its cloud condensation nuclei activity and interactions with marine clouds. Global climate models require new parameterizations of the SSA composition in order to improve the representation of these processes. Existing proposals for such a parameterization use remotely sensed chlorophyll a concentrations as a proxy for the biogenic contribution to the aerosol. However, both observations and theoretical considerations suggest that existing relationships with chlorophyll a, derived from observations at only a few locations, may not be representative for all ocean regions.

We introduce a novel framework for parameterizing the fractionation of marine organic matter into SSA based on a competitive Langmuir adsorption equilibrium at bubble surfaces. Marine organic matter is partitioned into classes with differing molecular weights, surface excesses, and Langmuir adsorption parameters. The classes include a lipid-like mixture associated with labile dissolved organic carbon (DOC), a polysaccharide-like mixture associated primarily with semilabile DOC, a protein-like mixture with concentrations intermediate between lipids and polysaccharides, a processed mixture associated with recalcitrant surface DOC, and a deep abyssal humic-like mixture.

Box model calculations have been performed for several cases of organic adsorption to illustrate the underlying concepts. We then apply the framework to output from a global marine biogeochemistry model, by partitioning total dissolved organic carbon into several classes of macromolecules. Each class is represented by model compounds with physical and chemical properties based on existing laboratory data. This allows us to globally map the predicted organic mass fraction of the nascent submicron sea spray aerosol.

Predicted relationships between chlorophyll a and organic fraction are similar to existing empirical parameterizations, but can vary between biologically productive and nonproductive regions, and seasonally within a given region. Major uncertainties include the bubble film thickness at bursting, and the variability of organic surfactant activity in the ocean, which is poorly constrained. In addition, polysaccharides may enter the aerosol more efficiently than Langmuir adsorption would suggest. Potential mechanisms for enrichment of polysaccharides in sea spray include the formation of marine colloidal particles that may be more efficiently swept up by rising bubbles, and cooperative adsorption of polysaccharides with proteins or lipids. These processes may make important contributions to the aerosol, but are not included here.

This organic fractionation framework is an initial step towards a closer linking of ocean biogeochemistry and aerosol chemical composition in Earth system models. Future work should focus on improving constraints on model parameters through new laboratory experiments or through empirical fitting to observed relationships in the real ocean and atmosphere, as well as on atmospheric implications of the variable composition of organic matter in sea spray.

Posted on 19 December 2014 | 12:00 am


Recent advances in understanding the Arctic climate system state and change from a sea ice perspective: a review

Recent advances in understanding the Arctic climate system state and change from a sea ice perspective: a review

Atmospheric Chemistry and Physics, 14, 13571-13600, 2014

Author(s): R. Döscher, T. Vihma, and E. Maksimovich

Sea ice is the central component and most sensitive indicator of the Arctic climate system. Both the depletion and areal decline of the Arctic sea ice cover, observed since the 1970s, have accelerated since the millennium. While the relationship of global warming to sea ice reduction is evident and underpinned statistically, it is the connecting mechanisms that are explored in detail in this review.

Sea ice erodes both from the top and the bottom. Atmospheric, oceanic and sea ice processes interact in non-linear ways on various scales. Feedback mechanisms lead to an Arctic amplification of the global warming system: the amplification is both supported by the ice depletion and, at the same time, accelerates ice reduction. Knowledge of the mechanisms of sea ice decline grew during the 1990s and deepened when the acceleration became clear in the early 2000s. Record minimum summer sea ice extents in 2002, 2005, 2007 and 2012 provide additional information on the mechanisms.

This article reviews recent progress in understanding the sea ice decline. Processes are revisited from atmospheric, oceanic and sea ice perspectives. There is strong evidence that decisive atmospheric changes are the major driver of sea ice change. Feedbacks due to reduced ice concentration, surface albedo, and ice thickness allow for additional local atmospheric and oceanic influences and self-supporting feedbacks. Large-scale ocean influences on Arctic Ocean hydrology and circulation are highly evident. Northward heat fluxes in the ocean are clearly impacting the ice margins, especially in the Atlantic sector of the Arctic. There is little indication of a direct and decisive influence of the warming ocean on the overall sea ice cover, due to an isolating layer of cold and fresh water underneath the sea ice.

Posted on 19 December 2014 | 12:00 am


Overview of the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT): mechanistic chamber studies on the oxidation of biogenic compounds

Overview of the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT): mechanistic chamber studies on the oxidation of biogenic compounds

Atmospheric Chemistry and Physics, 14, 13531-13549, 2014

Author(s): T. B. Nguyen, J. D. Crounse, R. H. Schwantes, A. P. Teng, K. H. Bates, X. Zhang, J. M. St. Clair, W. H. Brune, G. S. Tyndall, F. N. Keutsch, J. H. Seinfeld, and P. O. Wennberg

The Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT) was a collaborative atmospheric chamber campaign that occurred during January 2014. FIXCIT is the laboratory component of a synergistic field and laboratory effort aimed toward (1) better understanding the chemical details behind ambient observations relevant to the southeastern United States, (2) advancing the knowledge of atmospheric oxidation mechanisms of important biogenic hydrocarbons, and (3) characterizing the behavior of field instrumentation using authentic standards. Approximately 20 principal scientists from 14 academic and government institutions performed parallel measurements at a forested site in Alabama and at the atmospheric chambers at Caltech. During the 4 week campaign period, a series of chamber experiments was conducted to investigate the dark- and photo-induced oxidation of isoprene, ?-pinene, methacrolein, pinonaldehyde, acylperoxy nitrates, isoprene hydroxy nitrates (ISOPN), isoprene hydroxy hydroperoxides (ISOPOOH), and isoprene epoxydiols (IEPOX) in a highly controlled and atmospherically relevant manner. Pinonaldehyde and isomer-specific standards of ISOPN, ISOPOOH, and IEPOX were synthesized and contributed by campaign participants, which enabled explicit exploration into the oxidation mechanisms and instrument responses for these important atmospheric compounds. The present overview describes the goals, experimental design, instrumental techniques, and preliminary observations from the campaign. This work provides context for forthcoming publications affiliated with the FIXCIT campaign. Insights from FIXCIT are anticipated to aid significantly in interpretation of field data and the revision of mechanisms currently implemented in regional and global atmospheric models.

Posted on 19 December 2014 | 12:00 am


Radiocarbon analysis of elemental and organic carbon in Switzerland during winter-smog episodes from 2008 to 2012 – Part 1: Source apportionment and spatial variability

Radiocarbon analysis of elemental and organic carbon in Switzerland during winter-smog episodes from 2008 to 2012 – Part 1: Source apportionment and spatial variability

Atmospheric Chemistry and Physics, 14, 13551-13570, 2014

Author(s): P. Zotter, V. G. Ciobanu, Y. L. Zhang, I. El-Haddad, M. Macchia, K. R. Daellenbach, G. A. Salazar, R.-J. Huang, L. Wacker, C. Hueglin, A. Piazzalunga, P. Fermo, M. Schwikowski, U. Baltensperger, S. Szidat, and A. S. H. Prévôt

While several studies have investigated winter-time air pollution with a wide range of concentration levels, hardly any results are available for longer time periods covering several winter-smog episodes at various locations; e.g., often only a few weeks from a single winter are investigated. Here, we present source apportionment results of winter-smog episodes from 16 air pollution monitoring stations across Switzerland from five consecutive winters. Radiocarbon (14C) analyses of the elemental (EC) and organic (OC) carbon fractions, as well as levoglucosan, major water-soluble ionic species and gas-phase pollutant measurements were used to characterize the different sources of PM10. The most important contributions to PM10 during winter-smog episodes in Switzerland were on average the secondary inorganic constituents (sum of nitrate, sulfate and ammonium = 41 ± 15%) followed by organic matter (OM) (34 ± 13%) and EC (5 ± 2%). The non-fossil fractions of OC (fNF,OC) ranged on average from 69 to 85 and 80 to 95% for stations north and south of the Alps, respectively, showing that traffic contributes on average only up to ~ 30% to OC. The non-fossil fraction of EC (fNF,EC), entirely attributable to primary wood burning, was on average 42 ± 13 and 49 ± 15% for north and south of the Alps, respectively. While a high correlation was observed between fossil EC and nitrogen oxides, both primarily emitted by traffic, these species did not significantly correlate with fossil OC (OCF), which seems to suggest that a considerable amount of OCF is secondary, from fossil precursors. Elevated fNF,EC and fNF,OC values and the high correlation of the latter with other wood burning markers, including levoglucosan and water soluble potassium (K+) indicate that residential wood burning is the major source of carbonaceous aerosols during winter-smog episodes in Switzerland. The inspection of the non-fossil OC and EC levels and the relation with levoglucosan and water-soluble K+ shows different ratios for stations north and south of the Alps (most likely because of differences in burning technologies) for these two regions in Switzerland.

Posted on 19 December 2014 | 12:00 am


Aerosol radiative effects in the ultraviolet, visible, and near-infrared spectral ranges using long-term aerosol data series over the Iberian Peninsula

Aerosol radiative effects in the ultraviolet, visible, and near-infrared spectral ranges using long-term aerosol data series over the Iberian Peninsula

Atmospheric Chemistry and Physics, 14, 13497-13514, 2014

Author(s): D. Mateos, M. Antón, C. Toledano, V. E. Cachorro, L. Alados-Arboledas, M. Sorribas, M. J. Costa, and J. M. Baldasano

A better understanding of aerosol radiative properties is a crucial challenge for climate change studies. This study aims at providing a complete characterization of aerosol radiative effects in different spectral ranges within the shortwave (SW) solar spectrum. For this purpose, long-term data sets of aerosol properties from six AERONET stations located in the Iberian Peninsula (southwestern Europe) have been analyzed in terms of climatological characterization and inter-annual changes. Aerosol information was used as input for the libRadtran model in order to determine the aerosol radiative effect (ARE) at the surface in the ultraviolet (AREUV), visible (AREVIS), near-infrared (ARENIR), and the entire SW range (ARESW) under cloud-free conditions. Over the whole Iberian Peninsula, yearly aerosol radiative effects in the different spectral ranges were found to be ?1.1 < AREUV < ?0.7, ?5.7 < AREVIS < ?3.5, ?2.6 < ARENIR < ?1.6, and ?8.8 < ARESW < ?5.7 (in W m−2). Monthly means of ARE showed a seasonal pattern with larger values in spring and summer. The aerosol forcing efficiency (AFE), ARE per unit of aerosol optical depth, has also been evaluated in the four spectral ranges. AFE exhibited a dependence on single scattering albedo as well as a weaker one on the Ångström exponent. AFE is larger (in absolute value) for small and absorbing particles. The contributions of the UV, VIS, and NIR ranges to the SW efficiency varied with the aerosol types. The predominant aerosol size determined the fractions AFEVIS/AFESW and AFENIR/AFESW. The AFEVIS was the dominant contributor for all aerosol types, although non-absorbing large particles caused more even contribution of VIS and NIR intervals. The AFEUV / AFESW ratio showed a higher value in the case of absorbing fine particles.

Posted on 19 December 2014 | 12:00 am


Influence of CO2 observations on the optimized CO2 flux in an ensemble Kalman filter

Influence of CO2 observations on the optimized CO2 flux in an ensemble Kalman filter

Atmospheric Chemistry and Physics, 14, 13515-13530, 2014

Author(s): J. Kim, H. M. Kim, and C.-H. Cho

In this study, the effect of CO2 observations on an analysis of surface CO2 flux was calculated using an influence matrix in the CarbonTracker, which is an inverse modeling system for estimating surface CO2 flux based on an ensemble Kalman filter. The influence matrix represents a sensitivity of the analysis to observations. The experimental period was from January 2000 to December 2009. The diagonal element of the influence matrix (i.e., analysis sensitivity) is globally 4.8% on average, which implies that the analysis extracts 4.8% of the information from the observations and 95.2% from the background each assimilation cycle. Because the surface CO2 flux in each week is optimized by 5 weeks of observations, the cumulative impact over 5 weeks is 19.1%, much greater than 4.8%. The analysis sensitivity is inversely proportional to the number of observations used in the assimilation, which is distinctly apparent in continuous observation categories with a sufficient number of observations. The time series of the globally averaged analysis sensitivities shows seasonal variations, with greater sensitivities in summer and lower sensitivities in winter, which is attributed to the surface CO2 flux uncertainty. The time-averaged analysis sensitivities in the Northern Hemisphere are greater than those in the tropics and the Southern Hemisphere. The trace of the influence matrix (i.e., information content) is a measure of the total information extracted from the observations. The information content indicates an imbalance between the observation coverage in North America and that in other regions. Approximately half of the total observational information is provided by continuous observations, mainly from North America, which indicates that continuous observations are the most informative and that comprehensive coverage of additional observations in other regions is necessary to estimate the surface CO2 flux in these areas as accurately as in North America.

Posted on 19 December 2014 | 12:00 am


A global process-based study of marine CCN trends and variability

A global process-based study of marine CCN trends and variability

Atmospheric Chemistry and Physics, 14, 13631-13642, 2014

Author(s): E. M. Dunne, S. Mikkonen, H. Kokkola, and H. Korhonen

Low-level clouds have a strong climate-cooling effect in oceanic regions due to the much lower albedo of the underlying sea surface. Marine clouds typically have low droplet concentrations, making their radiative properties susceptible to changes in cloud condensation nucleus (CCN) concentrations. Here, we use the global aerosol model GLOMAP to investigate the processes that determine variations in marine CCN concentrations, and focus especially on the effects of previously identified wind speed trends in recent decades. Although earlier studies have found a link between linear wind speed trends and CCN concentration, we find that the effects of wind speed trends identified using a dynamic linear model in the Northern Equatorial Pacific (0.56 m s?1 per decade in the period 1990–2004) and the North Atlantic (?0.21 m s?1 per decade) are largely dampened by other processes controlling the CCN concentration, namely nucleation scavenging and transport of continental pollution. A CCN signal from wind speed change is seen only in the most pristine of the studied regions, i.e. over the Southern Ocean, where we simulate 3.4 cm?3 and 0.17 m s?1 increases over the 15-year period in the statistical mean levels of CCN and wind speed, respectively. Our results suggest that future changes in wind-speed-driven aerosol emissions from the oceans can probably have a climate feedback via clouds only in the most pristine regions. On the other hand, a feedback mechanism via changing precipitation patterns and intensities could take place over most oceanic regions, as we have shown that nucleation scavenging has by far the largest absolute effect on CCN concentrations.

Posted on 19 December 2014 | 12:00 am


Atmospheric submicron aerosol composition and particulate organic nitrate formation in a boreal forestland–urban mixed region

Atmospheric submicron aerosol composition and particulate organic nitrate formation in a boreal forestland–urban mixed region

Atmospheric Chemistry and Physics, 14, 13483-13495, 2014

Author(s): L. Q. Hao, A. Kortelainen, S. Romakkaniemi, H. Portin, A. Jaatinen, A. Leskinen, M. Komppula, P. Miettinen, D. Sueper, A. Pajunoja, J. N. Smith, K. E. J. Lehtinen, D. R. Worsnop, A. Laaksonen, and A. Virtanen

The Puijo aerosol–cloud observation station is a unique measurement site for its location in the mixed region between the boreal forestland and the municipality of Kuopio, Finland. A measurement campaign was carried out at the station during fall 2010. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-Tof-AMS) was deployed to characterize the atmospheric submicron aerosols. Positive matrix factorization (PMF) was applied to the unified high-resolution mass spectra organic species with NO+ and NO2+ ions to discover the intrinsic relationships between the organic and inorganic species and their daily cycles. On average, the submicron aerosols in this study were dominated by organic and sulfate species, composing 48.2 and 28.7% of total observed aerosol mass, respectively, with smaller contributions from ammonium (9.3%), nitrate (4.9%), chloride (0.8%) and BC (8.1%). The sources of these species included the primary emissions originating from the city area, secondary formation from both natural and anthropogenic emissions and regional transport. The PMF analysis succeeded in separating the mixed organic and inorganic spectra into three distinct organic and one inorganic factors. For organic factors, the semi-volatile oxygenated organic aerosol (SVOOA) and low-volatility oxygenated OA (LVOOA) accounted for 54.8 and 36.3% of total organic masses, respectively, while the hydrocarbon-like organic aerosol (HOA) accounted for 8.9% of total organics, with its main source from urban emissions. The inorganic factor is identified as NH4NO3, comprising 6.9% of the fitted aerosol mass by PMF. Based on the PMF results, the nitrate species were separated into organic and inorganic components, with the organic nitrates contributing one-third of the total nitrate mass. The results highlight both anthropogenic and biogenic emissions as important atmospheric aerosol sources in a forest–urban mixed region.

Posted on 18 December 2014 | 12:00 am


Dynamical analysis of sea-breeze hodograph rotation in Sardinia

Dynamical analysis of sea-breeze hodograph rotation in Sardinia

Atmospheric Chemistry and Physics, 14, 13471-13481, 2014

Author(s): N. Moisseeva and D. G. Steyn

This study investigates the diurnal evolution of sea-breeze (SB) rotation over an island at the middle latitudes. Earlier research on sea breezes in Sardinia shows that the onshore winds around various coasts of the island exhibit both the theoretically predicted clockwise rotation as well as seemingly anomalous anticlockwise rotation. A non-hydrostatic fully compressible numerical model (WRF) is used to simulate wind fields on and around the island on previously studied sea-breeze days, and is shown to capture the circulation on all coasts accurately. Diurnal rotation of wind is examined, and patterns of clockwise and anticlockwise rotation are identified. A dynamical analysis is performed by extracting individual forcing terms from the horizontal momentum equations. Analysis of several regions around the island shows that the direction of rotation is a result of a complex interaction between near-surface and synoptic pressure gradient, Coriolis and advection forcings. An idealized simulation is performed over an artificial island with dramatically simplified topography yet similar dimensions and latitude to Sardinia. Dynamical analysis of the idealized case reveals a rather different pattern of hodograph rotation to the real Sardinia, yet similar underlying dynamics. The research provides new insights into the dynamics underlying sea-breeze hodograph rotation, especially in coastal zones with a complex topography and/or coastline.

Posted on 18 December 2014 | 12:00 am


Reevaluation of stratospheric ozone trends from SAGE II data using a simultaneous temporal and spatial analysis

Reevaluation of stratospheric ozone trends from SAGE II data using a simultaneous temporal and spatial analysis

Atmospheric Chemistry and Physics, 14, 13455-13470, 2014

Author(s): R. P. Damadeo, J. M. Zawodny, and L. W. Thomason

This paper details a new method of regression for sparsely sampled data sets for use with time-series analysis, in particular the Stratospheric Aerosol and Gas Experiment (SAGE) II ozone data set. Non-uniform spatial, temporal, and diurnal sampling present in the data set result in biased values for the long-term trend if not accounted for. This new method is performed close to the native resolution of measurements and is a simultaneous temporal and spatial analysis that accounts for potential diurnal ozone variation. Results show biases, introduced by the way data are prepared for use with traditional methods, can be as high as 10%. Derived long-term changes show declines in ozone similar to other studies but very different trends in the presumed recovery period, with differences up to 2% per decade. The regression model allows for a variable turnaround time and reveals a hemispheric asymmetry in derived trends in the middle to upper stratosphere. Similar methodology is also applied to SAGE II aerosol optical depth data to create a new volcanic proxy that covers the SAGE II mission period. Ultimately this technique may be extensible towards the inclusion of multiple data sets without the need for homogenization.

Posted on 17 December 2014 | 12:00 am


Variability and trends in dynamical forcing of tropical lower stratospheric temperatures

Variability and trends in dynamical forcing of tropical lower stratospheric temperatures

Atmospheric Chemistry and Physics, 14, 13439-13453, 2014

Author(s): S. Fueglistaler, M. Abalos, T. J. Flannaghan, P. Lin, and W. J. Randel

The contribution of dynamical forcing to variations and trends in tropical lower stratospheric 70 hPa temperature for the period 1980–2011 is estimated based on ERA-Interim and Modern-Era Retrospective Analysis for Research and Applications (MERRA) reanalysis data. The dynamical forcing is estimated from the tropical mean residual upwelling calculated with the momentum balance equation, and with a simple proxy based on eddy heat fluxes averaged between 25° and 75° in both hemispheres. The thermodynamic energy equation with Newtonian cooling is used to relate the dynamical forcing to temperature. The deseasonalised, monthly mean time series of all four calculations are highly correlated (~ 0.85) with temperature for the period 1995–2011 when variations in radiatively active tracers are small. All four calculations provide additional support to previously noted prominent aspects of the temperature evolution 1980–2011: an anomalously strong dynamical cooling (~ ?1 to ?2 K) following the Pinatubo eruption that partially offsets the warming from enhanced aerosol, and a few years of enhanced dynamical cooling (~ ?0.4 K) after October 2000 that contributes to the prominent drop in water entering the stratosphere at that time. The time series of dynamically forced temperature calculated with the same method are more highly correlated and have more similar trends than those from the same reanalysis but with different methods. For 1980–2011 (without volcanic periods), the eddy heat flux calculations give a dynamical cooling of ~ ?0.1 to ~ ?0.25 K decade−1 (magnitude sensitive to latitude belt considered and reanalysis), largely due to increasing high latitude eddy heat flux trends in September and December–January. The eddy heat flux trends also explain the seasonality of temperature trends very well, with maximum cooling in January–February. Trends derived from momentum balance calculations show near-zero annual mean dynamical cooling, with weaker seasonal trends especially in December–January. These contradictory results arising from uncertainties in data and methods are discussed and put in context to previous analyses.

Posted on 17 December 2014 | 12:00 am


On the origin of the occasional spring nitrate peak in Greenland snow

On the origin of the occasional spring nitrate peak in Greenland snow

Atmospheric Chemistry and Physics, 14, 13361-13376, 2014

Author(s): L. Geng, J. Cole-Dai, B. Alexander, J. Erbland, J. Savarino, A. J. Schauer, E. J. Steig, P. Lin, Q. Fu, and M. C. Zatko

Ice core nitrate concentrations peak in the summer in both Greenland and Antarctica. Two nitrate concentration peaks in one annual layer have been observed some years in ice cores in Greenland from samples dating post-1900, with the additional nitrate peak occurring in the spring. The origin of the spring nitrate peak was hypothesized to be pollution transport from the mid-latitudes in the industrial era. We performed a case study on the origin of a spring nitrate peak in 2005 measured from a snowpit at Summit, Greenland, covering 3 years of snow accumulation. The effect of long-range transport of nitrate on this spring peak was excluded by using sulfate as a pollution tracer. The isotopic composition of nitrate (?15N, ?18O and ?17O) combined with photochemical calculations suggest that the occurrence of this spring peak is linked to a significantly weakened stratospheric ozone (O3) layer. The weakened O3 layer resulted in elevated UVB (ultraviolet-B) radiation on the snow surface, where the production of OH and NOx from the photolysis of their precursors was enhanced. Elevated NOx and OH concentrations resulted in enhanced nitrate production mainly through the NO2 + OH formation pathway, as indicated by decreases in ?18O and ?17O of nitrate associated with the spring peak. We further examined the nitrate concentration record from a shallow ice core covering the period from 1772 to 2006 and found 19 years with double nitrate peaks after the 1950s. Out of these 19 years, 14 of the secondary nitrate peaks were accompanied by sulfate peaks, suggesting long-range transport of nitrate as their source. In the other 5 years, low springtime O3 column density was observed, suggesting enhanced local production of nitrate as their source. The results suggest that, in addition to direct transport of nitrate from polluted regions, enhanced local photochemistry can also lead to a spring nitrate peak. The enhanced local photochemistry is probably associated with the interannual variability of O3 column density in the Arctic, which leads to elevated surface UV radiation in some years. In this scenario, enhanced photochemistry caused increased local nitrate production under the condition of elevated local NOx abundance in the industrial era.

Posted on 16 December 2014 | 12:00 am


Daily global fire radiative power fields estimation from one or two MODIS instruments

Daily global fire radiative power fields estimation from one or two MODIS instruments

Atmospheric Chemistry and Physics, 14, 13377-13390, 2014

Author(s): S. Remy and J. W. Kaiser

Fires are important emitters of aerosol and trace gases and as such need to be taken into account in any atmospheric composition modelling enterprise. One method to estimate these emissions is to convert fire radiative power (FRP) analysis into dry matter burnt and emissions of smoke constituents using land-cover-dependent conversion factors. Inventories like the Global Fire Assimilation System (GFAS) follow this approach by calculating daily global smoke emissions from FRP observed by the MODIS instruments onboard the Terra and Aqua satellites. Observations with different overpass times systematically sample fires at different stages in the strong diurnal fire cycle. For some time periods, observations are available from only one instrument, which leads to a bias in the observed average FRP.

We develop a method to correct this bias in daily FRP observations from any low Earth orbit (LEO) satellite, so that the budget of daily smoke emissions remains independent of the number of satellites from which FRP observations are taken into account. This ensures the possibility of running, for example, GFAS in case of failure of one of the MODIS instruments. It also enables the extension GFAS to 2000–2002 and the inclusion of FRP observations from upcoming satellite missions. The correction combines linear and non-linear regressions and uses an adaptive regionalization algorithm. It decreases the bias in daily average FRP from Terra and Aqua by more than 95%, and RMSE by 75% for Aqua and 55% for Terra. The correction algorithm is applied to Terra observations from 25 February 2000 to 31 December 2002, when Aqua observations were not available. The database of fire emissions GFASv1.0 is extended correspondingly.

Posted on 16 December 2014 | 12:00 am


Bromine partitioning in the tropical tropopause layer: implications for stratospheric injection

Bromine partitioning in the tropical tropopause layer: implications for stratospheric injection

Atmospheric Chemistry and Physics, 14, 13391-13410, 2014

Author(s): R. P. Fernandez, R. J. Salawitch, D. E. Kinnison, J.-F. Lamarque, and A. Saiz-Lopez

Very short-lived (VSL) bromocarbons are produced at a prodigious rate by ocean biology and these source compounds (SGVSL), together with their inorganic degradation products (PGVSL), are lofted by vigorous convection to the tropical tropopause layer (TTL). Using a state-of-the-art photochemical mechanism within a global model, we calculate annual average stratospheric injection of total bromine due to VSL sources to be 5 pptv (parts per trillion by volume), with ~ 3 pptv entering the stratosphere as PGVSL and ~ 2 pptv as SGVSL. The geographic distribution and partitioning of VSL bromine within the TTL, and its consequent stratospheric injection, is highly dependent on the oceanic flux, the strength of convection and the occurrence of heterogeneous recycling reactions. Our calculations indicate atomic Br should be the dominant inorganic species in large regions of the TTL during daytime, due to the low ozone and cold conditions of this region. We propose the existence of a "tropical ring of atomic bromine" located approximately between 15 and 19 km and between 30° N and 30° S. Daytime Br / BrO ratios of up to ~ 4 are predicted within this inhomogeneous ring in regions of highly convective transport, such as the tropical Western Pacific. Therefore, we suggest that experimental programs designed to quantify the bromine budget of the TTL and the stratospheric injection of VSL biogenic bromocarbons should include a strategy for the measurement of atomic Br during daytime as well as HOBr and BrCl during nighttime.

Posted on 16 December 2014 | 12:00 am


Long-term variability of dust events in Iceland (1949–2011)

Long-term variability of dust events in Iceland (1949–2011)

Atmospheric Chemistry and Physics, 14, 13411-13422, 2014

Author(s): P. Dagsson-Waldhauserova, O. Arnalds, and H. Olafsson

The long-term frequency of atmospheric dust observations was investigated for the southern part of Iceland and interpreted together with earlier results obtained from northeastern (NE) Iceland (Dagsson-Waldhauserova et al., 2013). In total, over 34 dust days per year on average occurred in Iceland based on conventionally used synoptic codes for dust observations. However, frequent volcanic eruptions, with the re-suspension of volcanic materials and dust haze, increased the number of dust events fourfold (135 dust days annually). The position of the Icelandic Low determined whether dust events occurred in the NE (16.4 dust days annually) or in the southern (S) part of Iceland (about 18 dust days annually). The decade with the most frequent dust days in S Iceland was the 1960s, but the 2000s in NE Iceland. A total of 32 severe dust storms (visibility < 500 m) were observed in Iceland with the highest frequency of events during the 2000s in S Iceland. The Arctic dust events (NE Iceland) were typically warm, occurring during summer/autumn (May–September) and during mild southwesterly winds, while the subarctic dust events (S Iceland) were mainly cold, occurring during winter/spring (March–May) and during strong northeasterly winds. About half of the dust events in S Iceland occurred in winter or at sub-zero temperatures. A good correlation was found between particulate matter (PM10) concentrations and visibility during dust observations at the stations Vík and Stórhöfði. This study shows that Iceland is among the dustiest areas of the world and that dust is emitted year-round.

Posted on 16 December 2014 | 12:00 am


Aerosol hygroscopicity and cloud condensation nuclei activity during the AC3Exp campaign: implications for cloud condensation nuclei parameterization

Aerosol hygroscopicity and cloud condensation nuclei activity during the AC3Exp campaign: implications for cloud condensation nuclei parameterization

Atmospheric Chemistry and Physics, 14, 13423-13437, 2014

Author(s): F. Zhang, Y. Li, Z. Li, L. Sun, R. Li, C. Zhao, P. Wang, Y. Sun, X. Liu, J. Li, P. Li, G. Ren, and T. Fan

Aerosol hygroscopicity and cloud condensation nuclei (CCN) activity under background conditions and during pollution events are investigated during the Aerosol-CCN-Cloud Closure Experiment (AC3Exp) campaign conducted at Xianghe, China in summer 2013. A gradual increase in size-resolved activation ratio (AR) with particle diameter (Dp) suggests that aerosol particles have different hygroscopicities. During pollution events, the activation diameter (Da) measured at low supersaturation (SS) was significantly increased compared to background conditions. An increase was not observed when SS was > 0.4%. The hygroscopicity parameter (?) was ~ 0.31–0.38 for particles in accumulation mode under background conditions. This range in magnitude of ? was ~ 20%, higher than ? derived under polluted conditions. For particles in nucleation or Aitken mode, ? ranged from 0.20–0.34 for background and polluted cases. Larger particles were on average more hygroscopic than smaller particles. The situation was more complex for heavy pollution particles because of the diversity in particle composition and mixing state. A non-parallel observation CCN closure test showed that uncertainties in CCN number concentration estimates ranged from 30–40%, which are associated with changes in particle composition as well as measurement uncertainties associated with bulk and size-resolved CCN methods. A case study showed that bulk CCN activation ratios increased as total condensation nuclei (CN) number concentrations (NCN) increased on background days. The background case also showed that bulk AR correlated well with the hygroscopicity parameter calculated from chemical volume fractions. On the contrary, bulk AR decreased with increasing total NCN during pollution events, but was closely related to the fraction of the total organic mass signal at m/z 44 (f44), which is usually associated with the particle's organic oxidation level. Our study highlights the importance of chemical composition in determining particle activation properties and underlines the significance of long-term observations of CCN under different atmospheric environments, especially regions with heavy pollution.

Posted on 16 December 2014 | 12:00 am


Long-term characterization of organic and elemental carbon in the PM2.5 fraction: the case of Athens, Greece

Long-term characterization of organic and elemental carbon in the PM2.5 fraction: the case of Athens, Greece

Atmospheric Chemistry and Physics, 14, 13313-13325, 2014

Author(s): D. Paraskevopoulou, E. Liakakou, E. Gerasopoulos, C. Theodosi, and N. Mihalopoulos

Organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC) and main ions were measured in a total of 1510 PM2.5 daily aerosol samples collected from May 2008 to April 2013 in Athens, Greece. OC and EC concentrations were 2.1 ± 1.3 ?g m?3 and 0.54 ± 0.39 ?g m?3, accounting for 11 ± 3% and 3 ± 1% of PM2.5 mass, respectively, with an average OC/EC ratio of 4.7 ± 3.1. Significant correlation was found between OC and EC during the whole period, indicating emissions by common primary sources on a regional scale. WSOC concentration ranged from 0.03 to 10.6 ?g m?3, with an average of 1.5 ± 0.9 ?g m?3. By considering the Finokalia (Crete) station as a reference, it was estimated that, during the warm season in Athens, 67 ± 7% of emitted OC and 53 ± 12% of emitted EC is regional, while, during cold months, the regional contribution of OC is only 33 ± 7% and of EC 29 ± 8%. Furthermore, secondary organic carbon (SOC) was calculated for the warm period of the year (April to October). The estimated SOC constituted about 75 ± 6% of PM2.5 organic carbon in Athens, highlighting significant aging processes on a regional scale. In the period 2011–2013 and during wintertime, an increase in OC and EC levels was observed, attributed to an increase in wood burning for domestic heating due to the economic crisis.

Posted on 15 December 2014 | 12:00 am


Emission of iodine-containing volatiles by selected microalgae species

Emission of iodine-containing volatiles by selected microalgae species

Atmospheric Chemistry and Physics, 14, 13327-13335, 2014

Author(s): U. R. Thorenz, L. J. Carpenter, R.-J. Huang, M. Kundel, J. Bosle, and T. Hoffmann

In this study we present the results of an emission study of different phytoplankton samples in aqueous media treated with elevated ozone levels. Halocarbon measurements show that the samples tested released bromoform and different iodocarbons, including iodomethane, iodochloromethane and diiodomethane. Iodide and iodate levels in the liquid phase were representative of concentrations of surface water in a natural environment. Measurement of volatile iodine (I2) emissions from two diatom samples (Mediopyxis helysia and Porosira glacialis) and the background sample (F/2 medium from filtered natural seawater) showed that the quantity of evolved I2 depends on the ozone concentration in the air. This behaviour was assumed to be caused by the oxidation reaction mechanism of iodide with ozone. The I2 emission flux agrees with model calculations at different iodide concentrations. The I2 emission of a natural plankton concentrate sample was, however, very low compared to other samples and showed no dependence on ozone. The reason for this was shown to be the low iodide concentration in the algal suspension, which seems to be the limiting factor in the oxidative formation of I2.

Posted on 15 December 2014 | 12:00 am


Meteorological factors controlling low-level continental pollutant outflow across a coast

Meteorological factors controlling low-level continental pollutant outflow across a coast

Atmospheric Chemistry and Physics, 14, 13295-13312, 2014

Author(s): D. L. Peake, H. F. Dacre, J. Methven, and O. Coceal

Coastal outflow describes the horizontal advection of pollutants from the continental boundary layer (BL) across a coastline. The outflow can ventilate polluted continental BLs and thus regulate air quality in highly populated coastal regions. This paper investigates the factors controlling coastal outflow and quantifies their importance as a ventilation mechanism. Tracers in the Met Office Unified Model (MetUM) are used to examine the magnitude and variability of coastal outflow over the eastern United States during summer 2004. Over the 4 week period examined, ventilation of tracer from the continental BL via coastal outflow occurs with the same magnitude as vertical ventilation via convection and advection. The relative importance of tracer decay rate, cross-coastal advection rate, and a parameter based on the relative continental and marine BL heights on coastal outflow is assessed by reducing the problem to a time-dependent box model. The ratio of the advection rate and decay rate is a dimensionless parameter which determines whether tracers are long-lived or short-lived. Long- and short-lived tracers exhibit different behaviours with respect to coastal outflow. Short-lived tracers exhibit large diurnal variability in coastal outflow but long-lived tracers do not. For short-lived tracers, increasing the advection rate increases the diurnally averaged magnitude of coastal outflow, but this has the opposite effect for very long-lived tracers. By using the box-model solutions to interpret the MetUM simulations, a land width is determined which represents the distance inland over which emissions contribute significantly to coastal outflow. A land width of between 100 and 400 km is found to be representative for a tracer with a lifetime of 24 h.

Posted on 15 December 2014 | 12:00 am


On the importance of cascading moisture recycling in South America

On the importance of cascading moisture recycling in South America

Atmospheric Chemistry and Physics, 14, 13337-13359, 2014

Author(s): D. C. Zemp, C.-F. Schleussner, H. M. J. Barbosa, R. J. van der Ent, J. F. Donges, J. Heinke, G. Sampaio, and A. Rammig

Continental moisture recycling is a crucial process of the South American climate system. In particular, evapotranspiration from the Amazon basin contributes substantially to precipitation regionally as well as over other remote regions such as the La Plata basin. Here we present an in-depth analysis of South American moisture recycling mechanisms. In particular, we quantify the importance of cascading moisture recycling (CMR), which describes moisture transport between two locations on the continent that involves re-evaporation cycles along the way. Using an Eulerian atmospheric moisture tracking model forced by a combination of several historical climate data sets, we were able to construct a complex network of moisture recycling for South America. Our results show that CMR contributes about 9–10% to the total precipitation over South America and 17–18% over the La Plata basin. CMR increases the fraction of total precipitation over the La Plata basin that originates from the Amazon basin from 18–23 to 24–29% during the wet season. We also show that the south-western part of the Amazon basin is not only a direct source of rainfall over the La Plata basin, but also a key intermediary region that distributes moisture originating from the entire Amazon basin towards the La Plata basin during the wet season. Our results suggest that land use change in this region might have a stronger impact on downwind rainfall than previously thought. Using complex network analysis techniques, we find the eastern side of the sub-tropical Andes to be a key region where CMR pathways are channeled. This study offers a better understanding of the interactions between the vegetation and the atmosphere on the water cycle, which is needed in a context of land use and climate change in South America.

Posted on 15 December 2014 | 12:00 am


A joint data assimilation system (Tan-Tracker) to simultaneously estimate surface CO2 fluxes and 3-D atmospheric CO2 concentrations from observations

A joint data assimilation system (Tan-Tracker) to simultaneously estimate surface CO2 fluxes and 3-D atmospheric CO2 concentrations from observations

Atmospheric Chemistry and Physics, 14, 13281-13293, 2014

Author(s): X. Tian, Z. Xie, Y. Liu, Z. Cai, Y. Fu, H. Zhang, and L. Feng

We have developed a novel framework ("Tan-Tracker") for assimilating observations of atmospheric CO2 concentrations, based on the POD-based (proper orthogonal decomposition) ensemble four-dimensional variational data assimilation method (PODEn4DVar). The high flexibility and the high computational efficiency of the PODEn4DVar approach allow us to include both the atmospheric CO2 concentrations and the surface CO2 fluxes as part of the large state vector to be simultaneously estimated from assimilation of atmospheric CO2 observations. Compared to most modern top-down flux inversion approaches, where only surface fluxes are considered as control variables, one major advantage of our joint data assimilation system is that, in principle, no assumption on perfect transport models is needed. In addition, the possibility for Tan-Tracker to use a complete dynamic model to consistently describe the time evolution of CO2 surface fluxes (CFs) and the atmospheric CO2 concentrations represents a better use of observation information for recycling the analyses at each assimilation step in order to improve the forecasts for the following assimilations. An experimental Tan-Tracker system has been built based on a complete augmented dynamical model, where (1) the surface atmosphere CO2 exchanges are prescribed by using a persistent forecasting model for the scaling factors of the first-guess net CO2 surface fluxes and (2) the atmospheric CO2 transport is simulated by using the GEOS-Chem three-dimensional global chemistry transport model. Observing system simulation experiments (OSSEs) for assimilating synthetic in situ observations of surface CO2 concentrations are carefully designed to evaluate the effectiveness of the Tan-Tracker system. In particular, detailed comparisons are made with its simplified version (referred to as TT-S) with only CFs taken as the prognostic variables. It is found that our Tan-Tracker system is capable of outperforming TT-S with higher assimilation precision for both CO2 concentrations and CO2 fluxes, mainly due to the simultaneous estimation of CO2 concentrations and CFs in our Tan-Tracker data assimilation system. A experiment for assimilating the real dry-air column CO2 retrievals (XCO2) from the Japanese Greenhouse Gases Observation Satellite (GOSAT) further demonstrates its potential wide applications.

Posted on 12 December 2014 | 12:00 am


Comparison of the HadGEM2 climate-chemistry model against in situ and SCIAMACHY atmospheric methane data

Comparison of the HadGEM2 climate-chemistry model against in situ and SCIAMACHY atmospheric methane data

Atmospheric Chemistry and Physics, 14, 13257-13280, 2014

Author(s): G. D. Hayman, F. M. O'Connor, M. Dalvi, D. B. Clark, N. Gedney, C. Huntingford, C. Prigent, M. Buchwitz, O. Schneising, J. P. Burrows, C. Wilson, N. Richards, and M. Chipperfield

Wetlands are a major emission source of methane (CH4) globally. In this study, we evaluate wetland emission estimates derived using the UK community land surface model (JULES, the Joint UK Land Earth Simulator) against atmospheric observations of methane, including, for the first time, total methane columns derived from the SCIAMACHY instrument on board the ENVISAT satellite.

Two JULES wetland emission estimates are investigated: (a) from an offline run driven with Climatic Research Unit–National Centers for Environmental Prediction (CRU-NCEP) meteorological data and (b) from the same offline run in which the modelled wetland fractions are replaced with those derived from the Global Inundation Extent from Multi-Satellites (GIEMS) remote sensing product. The mean annual emission assumed for each inventory (181 Tg CH4 per annum over the period 1999–2007) is in line with other recently published estimates. There are regional differences as the unconstrained JULES inventory gives significantly higher emissions in the Amazon (by ~36 Tg CH4 yr−1) and lower emissions in other regions (by up to 10 Tg CH4 yr−1) compared to the JULES estimates constrained with the GIEMS product.

Using the UK Hadley Centre's Earth System model with atmospheric chemistry (HadGEM2), we evaluate these JULES wetland emissions against atmospheric observations of methane. We obtain improved agreement with the surface concentration measurements, especially at high northern latitudes, compared to previous HadGEM2 runs using the wetland emission data set of Fung et al. (1991). Although the modelled monthly atmospheric methane columns reproduce the large-scale patterns in the SCIAMACHY observations, they are biased low by 50 part per billion by volume (ppb). Replacing the HadGEM2 modelled concentrations above 300 hPa with HALOE–ACE assimilated TOMCAT output results in a significantly better agreement with the SCIAMACHY observations. The use of the GIEMS product to constrain the JULES-derived wetland fraction improves the representation of the wetland emissions in JULES and gives a good description of the seasonality observed at surface sites influenced by wetlands, especially at high latitudes. We find that the annual cycles observed in the SCIAMACHY measurements and at many of the surface sites influenced by non-wetland sources cannot be reproduced in these HadGEM2 runs. This suggests that the emissions over certain regions (e.g. India and China) are possibly too high and/or the monthly emission patterns for specific sectors are incorrect.

The comparisons presented in this paper show that the performance of the JULES wetland scheme is comparable to that of other process-based land surface models. We identify areas for improvement in this and the atmospheric chemistry components of the HadGEM Earth System model. The Earth Observation data sets used here will be of continued value in future evaluations of JULES and the HadGEM family of models.

Posted on 12 December 2014 | 12:00 am


Novel methods for predicting gas–particle partitioning during the formation of secondary organic aerosol

Novel methods for predicting gas–particle partitioning during the formation of secondary organic aerosol

Atmospheric Chemistry and Physics, 14, 13189-13204, 2014

Author(s): F. Wania, Y. D. Lei, C. Wang, J. P. D. Abbatt, and K.-U. Goss

Several methods have been presented in the literature to predict an organic chemical's equilibrium partitioning between the water insoluble organic matter (WIOM) component of aerosol and the gas phase, Ki,WIOM, as a function of temperature. They include (i) polyparameter linear free energy relationships calibrated with empirical aerosol sorption data, as well as (ii) the solvation models implemented in SPARC and (iii) the quantum-chemical software COSMOtherm, which predict solvation equilibria from molecular structure alone. We demonstrate that these methods can be used to predict Ki,WIOM for large numbers of individual molecules implicated in secondary organic aerosol (SOA) formation, including those with multiple functional groups. Although very different in their theoretical foundations, these methods give remarkably consistent results for the products of the reaction of normal alkanes with OH, i.e. their partition coefficients Ki,WIOM generally agree within one order of magnitude over a range of more than ten orders of magnitude. This level of agreement is much better than that achieved by different vapour pressure estimation methods that are more commonly used in the SOA community. Also, in contrast to the agreement between vapour pressure estimates, the agreement between the Ki,WIOM estimates does not deteriorate with increasing number of functional groups. Furthermore, these partitioning coefficients Ki,WIOM predicted SOA mass yields in agreement with those measured in chamber experiments of the oxidation of normal alkanes. If a Ki,WIOM prediction method was based on one or more surrogate molecules representing the solvation properties of the mixed OM phase of SOA, the choice of those molecule(s) was found to have a relatively minor effect on the predicted Ki,WIOM, as long as the molecule(s) are not very polar. This suggests that a single surrogate molecule, such as 1-octanol or a hypothetical SOA structure proposed by Kalberer et al. (2004), may often be sufficient to represent the WIOM component of the SOA phase, greatly simplifying the prediction. The presented methods could substitute for vapour-pressure-based methods in studies such as the explicit modelling of SOA formation from single precursor molecules in chamber experiments.

Posted on 11 December 2014 | 12:00 am


Tropical deep convective life cycle: Cb-anvil cloud microphysics from high-altitude aircraft observations

Tropical deep convective life cycle: Cb-anvil cloud microphysics from high-altitude aircraft observations

Atmospheric Chemistry and Physics, 14, 13223-13240, 2014

Author(s): W. Frey, S. Borrmann, F. Fierli, R. Weigel, V. Mitev, R. Matthey, F. Ravegnani, N. M. Sitnikov, A. Ulanovsky, and F. Cairo

The case study presented here focuses on the life cycle of clouds in the anvil region of a tropical deep convective system. During the SCOUT-O3 campaign from Darwin, Northern Australia, the Hector storm system has been probed by the Geophysica high-altitude aircraft. Clouds were observed by in situ particle probes, a backscatter sonde, and a miniature lidar. Additionally, aerosol number concentrations have been measured. On 30 November 2005 a double flight took place and Hector was probed throughout its life cycle in its developing, mature, and dissipating stage. The two flights were four hours apart and focused on the anvil region of Hector in altitudes between 10.5 and 18.8 km (i.e. above 350 K potential temperature). Trajectory calculations, satellite imagery, and ozone measurements have been used to ensure that the same cloud air masses have been probed in both flights.

The size distributions derived from the measurements show a change not only with increasing altitude but also with the evolution of Hector. Clearly different cloud to aerosol particle ratios as well as varying ice crystal morphology have been found for the different development stages of Hector, indicating different freezing mechanisms. The development phase exhibits the smallest ice particles (up to 300 ?m) with a rather uniform morphology. This is indicative for rapid glaciation during Hector's development. Sizes of ice crystals are largest in the mature stage (larger than 1.6 mm) and even exceed those of some continental tropical deep convective clouds, also in their number concentrations. The backscatter properties and particle images show a change in ice crystal shape from the developing phase to rimed and aggregated particles in the mature and dissipating stages; the specific shape of particles in the developing phase cannot be distinguished from the measurements. Although optically thin, the clouds in the dissipating stage have a large vertical extent (roughly 6 km) and persist for at least 6 h. Thus, the anvils of these high-reaching deep convective clouds have a high potential for affecting the tropical tropopause layer by modifying the humidity and radiative budget, as well as for providing favourable conditions for subvisible cirrus formation. The involved processes may also influence the amount of water vapour that ultimately reaches the stratosphere in the tropics.

Posted on 11 December 2014 | 12:00 am


Technical Note: Reanalysis of upper troposphere humidity data from the MOZAIC programme for the period 1994 to 2009

Technical Note: Reanalysis of upper troposphere humidity data from the MOZAIC programme for the period 1994 to 2009

Atmospheric Chemistry and Physics, 14, 13241-13255, 2014

Author(s): H. G. J. Smit, S. Rohs, P. Neis, D. Boulanger, M. Krämer, A. Wahner, and A. Petzold

In situ observational data on the relative humidity (RH) in the upper troposphere and lowermost stratosphere (UT/LS), or tropopause region, collected aboard civil passenger aircraft in the MOZAIC (Measurements of OZone, water vapour, carbon monoxide and nitrogen oxides by in-service AIrbus airCraft) programme were reanalysed for the period 2000 to 2009. Previous analyses of probability distribution functions (PDFs) of upper troposphere humidity (UTH) data from MOZAIC observations from year 2000 and later indicated a bias of UTH data towards higher RH values compared to data of the period 1994 to 1999. As a result, the PDF of UTH data show a substantial fraction of observations above 100% relative humidity with respect to liquid water. Such supersaturations, however, do not occur in the atmosphere because there is always a sufficient number of condensation nuclei available, that trigger condensation as soon as liquid saturation is slightly exceeded. An in-depth reanalysis of the data set identified a coding error in the calibration procedure from year 2000 on. The error did not affect earlier data from 1994 to 1999. The full data set for 2000–2009 was reanalysed applying the corrected calibration procedure. Applied correction schemes and a revised error analysis are presented along with the reanalysed PDF of relative humidity with respect to liquid water (RHliquid) and ice (RHice).

Posted on 11 December 2014 | 12:00 am


Determination and climatology of the planetary boundary layer height above the Swiss plateau by in situ and remote sensing measurements as well as by the COSMO-2 model

Determination and climatology of the planetary boundary layer height above the Swiss plateau by in situ and remote sensing measurements as well as by the COSMO-2 model

Atmospheric Chemistry and Physics, 14, 13205-13221, 2014

Author(s): M. Collaud Coen, C. Praz, A. Haefele, D. Ruffieux, P. Kaufmann, and B. Calpini

The planetary boundary layer (PBL) height is a key parameter in air quality control and pollutant dispersion. The PBL height cannot, however, be directly measured, and its estimation relies on the analysis of the vertical profiles of the temperature, turbulence or the atmospheric composition. An operational PBL height detection method including several remote sensing instruments (wind profiler, Raman lidar, microwave radiometer) and several algorithms (Parcel and bulk Richardson number methods, surface-based temperature inversion, aerosol or humidity gradient analysis) was developed and tested with 1 year of measurements, which allows the methods to be validated against radio sounding measurements. The microwave radiometer provides convective boundary layer heights in good agreement with the radio sounding (RS) (median bias < 25 m, R2 > 0.70) and allows the analysis of the diurnal variation of the PBL height due to its high temporal resolution. The Raman lidar also leads to a good agreement with RS, whereas the wind profiler yields some more dispersed results mostly due to false attribution problems. A comparison with the numerical weather prediction model COSMO-2 has shown a general overestimation of the model PBL height by some hundreds to thousand meters. Finally the seasonal cycles of the daytime and nighttime PBL heights are discussed for each instrument and each detection algorithm for two stations on the Swiss plateau.

Posted on 11 December 2014 | 12:00 am


Ground-level ozone in four Chinese cities: precursors, regional transport and heterogeneous processes

Ground-level ozone in four Chinese cities: precursors, regional transport and heterogeneous processes

Atmospheric Chemistry and Physics, 14, 13175-13188, 2014

Author(s): L. K. Xue, T. Wang, J. Gao, A. J. Ding, X. H. Zhou, D. R. Blake, X. F. Wang, S. M. Saunders, S. J. Fan, H. C. Zuo, Q. Z. Zhang, and W. X. Wang

We analyzed the measurements of ozone (O3) and its precursors made at rural/suburban sites downwind of four large Chinese cities – Beijing, Shanghai, Guangzhou and Lanzhou, to elucidate their pollution characteristics, regional transport, in situ production, and impacts of heterogeneous processes. The same measurement techniques and observation-based model were used to minimize uncertainties in comparison of the results due to difference in methodologies. All four cities suffered from serious O3 pollution but showed different precursor distributions. The model-calculated in situ O3 production rates were compared with the observed change rates to infer the relative contributions of on-site photochemistry and transport. At the rural site downwind of Beijing, export of the well-processed urban plumes contributed to the extremely high O3 levels (up to an hourly value of 286 ppbv), while the O3 pollution observed at suburban sites of Shanghai, Guangzhou and Lanzhou was dominated by intense in situ production. The O3 production was in a volatile organic compound (VOC)-limited regime in both Shanghai and Guangzhou, and a NOx-limited regime in Lanzhou. The key VOC precursors are aromatics and alkenes in Shanghai, and aromatics in Guangzhou. The potential impacts on O3 production of several heterogeneous processes, namely, hydrolysis of dinitrogen pentoxide (N2O5), uptake of hydro peroxy radical (HO2) on particles and surface reactions of NO2 forming nitrous acid (HONO), were assessed. The analyses indicate the varying and considerable impacts of these processes in different areas of China depending on the atmospheric abundances of aerosol and NOx, and suggest the urgent need to better understand these processes and represent them in photochemical models.

Posted on 10 December 2014 | 12:00 am


A comprehensive parameterization of heterogeneous ice nucleation of dust surrogate: laboratory study with hematite particles and its application to atmospheric models

A comprehensive parameterization of heterogeneous ice nucleation of dust surrogate: laboratory study with hematite particles and its application to atmospheric models

Atmospheric Chemistry and Physics, 14, 13145-13158, 2014

Author(s): N. Hiranuma, M. Paukert, I. Steinke, K. Zhang, G. Kulkarni, C. Hoose, M. Schnaiter, H. Saathoff, and O. Möhler

A new heterogeneous ice nucleation parameterization that covers a wide temperature range (?36 to ?78 °C) is presented. Developing and testing such an ice nucleation parameterization, which is constrained through identical experimental conditions, is important to accurately simulate the ice nucleation processes in cirrus clouds. The ice nucleation active surface-site density (ns) of hematite particles, used as a proxy for atmospheric dust particles, were derived from AIDA (Aerosol Interaction and Dynamics in the Atmosphere) cloud chamber measurements under water subsaturated conditions. These conditions were achieved by continuously changing the temperature (T) and relative humidity with respect to ice (RHice) in the chamber. Our measurements showed several different pathways to nucleate ice depending on T and RHice conditions. For instance, almost T-independent freezing was observed at ?60 °C < T < ?50 °C, where RHice explicitly controlled ice nucleation efficiency, while both T and RHice played roles in other two T regimes: ?78 °C < T < ?60 °C and ?50 °C < T < ?36 °C. More specifically, observations at T lower than ?60 °C revealed that higher RHice was necessary to maintain a constant ns, whereas T may have played a significant role in ice nucleation at T higher than ?50 °C. We implemented the new hematite-derived ns parameterization, which agrees well with previous AIDA measurements of desert dust, into two conceptual cloud models to investigate their sensitivity to the new parameterization in comparison to existing ice nucleation schemes for simulating cirrus cloud properties. Our results show that the new AIDA-based parameterization leads to an order of magnitude higher ice crystal concentrations and to an inhibition of homogeneous nucleation in lower-temperature regions. Our cloud simulation results suggest that atmospheric dust particles that form ice nuclei at lower temperatures, below ?36 °C, can potentially have a stronger influence on cloud properties, such as cloud longevity and initiation, compared to previous parameterizations.

Posted on 10 December 2014 | 12:00 am


Development of a 10-year (2001–2010) 0.1° data set of land-surface energy balance for mainland China

Development of a 10-year (2001–2010) 0.1° data set of land-surface energy balance for mainland China

Atmospheric Chemistry and Physics, 14, 13097-13117, 2014

Author(s): X. Chen, Z. Su, Y. Ma, S. Liu, Q. Yu, and Z. Xu

In the absence of high-resolution estimates of the components of surface energy balance for China, we developed an algorithm based on the surface energy balance system (SEBS) to generate a data set of land-surface energy and water fluxes on a monthly timescale from 2001 to 2010 at a 0.1 × 0.1° spatial resolution by using multi-satellite and meteorological forcing data. A remote-sensing-based method was developed to estimate canopy height, which was used to calculate roughness length and flux dynamics. The land-surface flux data set was validated against "ground-truth" observations from 11 flux tower stations in China. The estimated fluxes correlate well with the stations' measurements for different vegetation types and climatic conditions (average bias = 11.2 Wm?2, RMSE = 22.7 Wm?2). The quality of the data product was also assessed against the GLDAS data set. The results show that our method is efficient for producing a high-resolution data set of surface energy flux for the Chinese landmass from satellite data. The validation results demonstrate that more accurate downward long-wave radiation data sets are needed to be able to estimate turbulent fluxes and evapotranspiration accurately when using the surface energy balance model. Trend analysis of land-surface radiation and energy exchange fluxes revealed that the Tibetan Plateau has undergone relatively stronger climatic change than other parts of China during the last 10 years. The capability of the data set to provide spatial and temporal information on water-cycle and land–atmosphere interactions for the Chinese landmass is examined. The product is free to download for studies of the water cycle and environmental change in China.

Posted on 10 December 2014 | 12:00 am


Iodine chemistry in the troposphere and its effect on ozone

Iodine chemistry in the troposphere and its effect on ozone

Atmospheric Chemistry and Physics, 14, 13119-13143, 2014

Author(s): A. Saiz-Lopez, R. P. Fernandez, C. Ordóñez, D. E. Kinnison, J. C. Gómez Martín, J.-F. Lamarque, and S. Tilmes

Despite the potential influence of iodine chemistry on the oxidizing capacity of the troposphere, reactive iodine distributions and their impact on tropospheric ozone remain almost unexplored aspects of the global atmosphere. Here we present a comprehensive global modelling experiment aimed at estimating lower and upper limits of the inorganic iodine burden and its impact on tropospheric ozone. Two sets of simulations without and with the photolysis of IxOy oxides (i.e. I2O2, I2O3 and I2O4) were conducted to define the range of inorganic iodine loading, partitioning and impact in the troposphere. Our results show that the most abundant daytime iodine species throughout the middle to upper troposphere is atomic iodine, with an annual average tropical abundance of (0.15–0.55) pptv. We propose the existence of a "tropical ring of atomic iodine" that peaks in the tropical upper troposphere (~11–14 km) at the equator and extends to the sub-tropics (30° N–30° S). Annual average daytime I / IO ratios larger than 3 are modelled within the tropics, reaching ratios up to ~20 during vigorous uplift events within strong convective regions. We calculate that the integrated contribution of catalytic iodine reactions to the total rate of tropospheric ozone loss (IOx Loss) is 2–5 times larger than the combined bromine and chlorine cycles. When IxOy photolysis is included, IOx Loss represents an upper limit of approximately 27, 14 and 27% of the tropical annual ozone loss for the marine boundary layer (MBL), free troposphere (FT) and upper troposphere (UT), respectively, while the lower limit throughout the tropical troposphere is ~9%. Our results indicate that iodine is the second strongest ozone-depleting family throughout the global marine UT and in the tropical MBL. We suggest that (i) iodine sources and its chemistry need to be included in global tropospheric chemistry models, (ii) experimental programs designed to quantify the iodine budget in the troposphere should include a strategy for the measurement of atomic I, and (iii) laboratory programs are needed to characterize the photochemistry of higher iodine oxides to determine their atmospheric fate since they can potentially dominate halogen-catalysed ozone destruction in the troposphere.

Posted on 10 December 2014 | 12:00 am


Methane and carbon dioxide fluxes and their regional scalability for the European Arctic wetlands during the MAMM project in summer 2012

Methane and carbon dioxide fluxes and their regional scalability for the European Arctic wetlands during the MAMM project in summer 2012

Atmospheric Chemistry and Physics, 14, 13159-13174, 2014

Author(s): S. J. O'Shea, G. Allen, M. W. Gallagher, K. Bower, S. M. Illingworth, J. B. A. Muller, B. T. Jones, C. J. Percival, S. J-B. Bauguitte, M. Cain, N. Warwick, A. Quiquet, U. Skiba, J. Drewer, K. Dinsmore, E. G. Nisbet, D. Lowry, R. E. Fisher, J. L. France, M. Aurela, A. Lohila, G. Hayman, C. George, D. B. Clark, A. J. Manning, A. D. Friend, and J. Pyle

Airborne and ground-based measurements of methane (CH4), carbon dioxide (CO2) and boundary layer thermodynamics were recorded over the Fennoscandian landscape (67–69.5° N, 20–28° E) in July 2012 as part of the MAMM (Methane and other greenhouse gases in the Arctic: Measurements, process studies and Modelling) field campaign. Employing these airborne measurements and a simple boundary layer box model, net regional-scale (~ 100 km) fluxes were calculated to be 1.2 ± 0.5 mg CH4 h?1 m?2 and ?350 ± 143 mg CO2 h?1 m?2. These airborne fluxes were found to be relatively consistent with seasonally averaged surface chamber (1.3 ± 1.0 mg CH4 h?1 m?2) and eddy covariance (1.3 ± 0.3 mg CH4 h?1 m?2 and ?309 ± 306 mg CO2 h?1 m−2) flux measurements in the local area. The internal consistency of the aircraft-derived fluxes across a wide swath of Fennoscandia coupled with an excellent statistical comparison with local seasonally averaged ground-based measurements demonstrates the potential scalability of such localised measurements to regional-scale representativeness. Comparisons were also made to longer-term regional CH4 climatologies from the JULES (Joint UK Land Environment Simulator) and HYBRID8 land surface models within the area of the MAMM campaign. The average hourly emission flux output for the summer period (July–August) for the year 2012 was 0.084 mg CH4 h?1 m?2 (minimum 0.0 and maximum 0.21 mg CH4 h?1 m?2) for the JULES model and 0.088 mg CH4 h?1 m?2 (minimum 0.0008 and maximum 1.53 mg CH4 h?1 m?2) for HYBRID8. Based on these observations both models were found to significantly underestimate the CH4 emission flux in this region, which was linked to the under-prediction of the wetland extents generated by the models.

Posted on 10 December 2014 | 12:00 am


The impact of volcanic aerosol on the Northern Hemisphere stratospheric polar vortex: mechanisms and sensitivity to forcing structure

The impact of volcanic aerosol on the Northern Hemisphere stratospheric polar vortex: mechanisms and sensitivity to forcing structure

Atmospheric Chemistry and Physics, 14, 13063-13079, 2014

Author(s): M. Toohey, K. Krüger, M. Bittner, C. Timmreck, and H. Schmidt

Observations and simple theoretical arguments suggest that the Northern Hemisphere (NH) stratospheric polar vortex is stronger in winters following major volcanic eruptions. However, recent studies show that climate models forced by prescribed volcanic aerosol fields fail to reproduce this effect. We investigate the impact of volcanic aerosol forcing on stratospheric dynamics, including the strength of the NH polar vortex, in ensemble simulations with the Max Planck Institute Earth System Model. The model is forced by four different prescribed forcing sets representing the radiative properties of stratospheric aerosol following the 1991 eruption of Mt. Pinatubo: two forcing sets are based on observations, and are commonly used in climate model simulations, and two forcing sets are constructed based on coupled aerosol–climate model simulations. For all forcings, we find that simulated temperature and zonal wind anomalies in the NH high latitudes are not directly impacted by anomalous volcanic aerosol heating. Instead, high-latitude effects result from enhancements in stratospheric residual circulation, which in turn result, at least in part, from enhanced stratospheric wave activity. High-latitude effects are therefore much less robust than would be expected if they were the direct result of aerosol heating. Both observation-based forcing sets result in insignificant changes in vortex strength. For the model-based forcing sets, the vortex response is found to be sensitive to the structure of the forcing, with one forcing set leading to significant strengthening of the polar vortex in rough agreement with observation-based expectations. Differences in the dynamical response to the forcing sets imply that reproducing the polar vortex responses to past eruptions, or predicting the response to future eruptions, depends on accurate representation of the space–time structure of the volcanic aerosol forcing.

Posted on 9 December 2014 | 12:00 am


An improved dust emission model – Part 2: Evaluation in the Community Earth System Model, with implications for the use of dust source functions

An improved dust emission model – Part 2: Evaluation in the Community Earth System Model, with implications for the use of dust source functions

Atmospheric Chemistry and Physics, 14, 13043-13061, 2014

Author(s): J. F. Kok, S. Albani, N. M. Mahowald, and D. S. Ward

The complex nature of mineral dust aerosol emission makes it a difficult process to represent accurately in weather and climate models. Indeed, results in the companion paper indicate that many large-scale models underestimate the dust flux's sensitivity to the soil's threshold friction velocity for erosion. We hypothesize that this finding explains why many dust cycle simulations are improved by using an empirical dust source function that shifts emissions towards the world's most erodible regions. Here, we both test this hypothesis and evaluate the performance of the new dust emission parameterization presented in the companion paper. We do so by implementing the new emission scheme into the Community Earth System Model (CESM) and comparing the resulting dust cycle simulations against an array of measurements. We find that the new scheme shifts emissions towards the world's most erodible regions in a manner that is strikingly similar to the effect of implementing a widely used source function based on satellite observations of dust source regions. Furthermore, model comparisons against aerosol optical depth measurements show that the new physically based scheme produces a statistically significant improvement in CESM's representation of dust emission, which exceeds the improvement produced by implementing a source function. These results indicate that the need to use an empirical source function is eliminated, at least in CESM, by the additional physics in the new scheme, and in particular by its increased sensitivity to the soil's threshold friction velocity. Since the threshold friction velocity is affected by climate changes, our results further suggest that many large-scale models underestimate the global dust cycle's climate sensitivity.

Posted on 9 December 2014 | 12:00 am


A model study on changes of European and Swiss particulate matter, ozone and nitrogen deposition between 1990 and 2020 due to the revised Gothenburg protocol

A model study on changes of European and Swiss particulate matter, ozone and nitrogen deposition between 1990 and 2020 due to the revised Gothenburg protocol

Atmospheric Chemistry and Physics, 14, 13081-13095, 2014

Author(s): S. Aksoyoglu, J. Keller, G. Ciarelli, A. S. H. Prévôt, and U. Baltensperger

We report a study of changes in air quality due to emission reductions using the chemical transport model CAMx. The model domain includes all of Europe with a nested domain over Switzerland. The model simulations were performed with emissions for 1990 (the reference year for the Gothenburg Protocol), 2005 (the reference year for the revised Gothenburg Protocol), 2006 (for model validation) and 2020 (the target year for the revised Gothenburg Protocol) using three emission scenarios prepared by IIASA/GAINS. Changes in ozone, particulate matter and nitrogen deposition are the central theme of the study.

The modelled relative changes in the annual average PM2.5 concentrations between 1990 and 2005 look reasonable based on various PM10 and PM2.5 observations in the past. The results obtained in this study suggest that annual mean concentrations of PM2.5 decreased by about 20–50% in Europe. Simulations using the baseline scenario (BL 2020) suggest that PM2.5 concentrations in 2020 will be about 30% lower than those in 2005. The largest predicted decrease in PM2.5, based on the MTFR (maximum technically feasible reduction) scenario, was about 60% and was located mainly in the eastern part of Europe.

In the case of ozone, both model results and measurements show an increase in the mean ozone mixing ratios between 1990 and 2005. The observations, however, suggest a larger increase, indicating the importance of background ozone levels. Although emission reductions caused a decrease in peak ozone values, average ozone levels in polluted regions increased due to reduced titration with nitric oxide (NO). This caused a change in the frequency distribution of ozone. Model simulations using emission scenarios for 2020 suggest that annual average ozone mixing ratios will continue to increase. Changes in the levels of the damage indicators AOT40 for forests and SOMO35 are reported as well.

The model results suggest that nitrogen deposition has decreased by 10–30% in the eastern part of Europe since 1990, while it has increased by about 20% in the Iberian Peninsula. The decrease is mainly due to the deposition of oxidized nitrogen species, whereas deposition of reduced nitrogen compounds increased. In Switzerland, nitrogen deposition is larger in the northern part of the Alps, where ammonia emissions are the highest. Applying the baseline scenario, we found that the deposition of oxidized nitrogen compounds will have decreased by a further 40% by 2020, whereas deposition of reduced species will continue to increase. This will lead to a 10–20% decrease in the total nitrogen deposition in most of the model domain, with a 10% increase in the eastern part of Europe.

Posted on 9 December 2014 | 12:00 am


An improved dust emission model – Part 1: Model description and comparison against measurements

An improved dust emission model – Part 1: Model description and comparison against measurements

Atmospheric Chemistry and Physics, 14, 13023-13041, 2014

Author(s): J. F. Kok, N. M. Mahowald, G. Fratini, J. A. Gillies, M. Ishizuka, J. F. Leys, M. Mikami, M.-S. Park, S.-U. Park, R. S. Van Pelt, and T. M. Zobeck

Simulations of the dust cycle and its interactions with the changing Earth system are hindered by the empirical nature of dust emission parameterizations in weather and climate models. Here we take a step towards improving dust cycle simulations by using a combination of theory and numerical simulations to derive a physically based dust emission parameterization. Our parameterization is straightforward to implement into large-scale models, as it depends only on the wind friction velocity and the soil's threshold friction velocity. Moreover, it accounts for two processes missing from most existing parameterizations: a soil's increased ability to produce dust under saltation bombardment as it becomes more erodible, and the increased scaling of the dust flux with wind speed as a soil becomes less erodible. Our treatment of both these processes is supported by a compilation of quality-controlled vertical dust flux measurements. Furthermore, our scheme reproduces this measurement compilation with substantially less error than the existing dust flux parameterizations we were able to compare against. A critical insight from both our theory and the measurement compilation is that dust fluxes are substantially more sensitive to the soil's threshold friction velocity than most current schemes account for.

Posted on 9 December 2014 | 12:00 am


Rare temperature histories and cirrus ice number density in a parcel and a one-dimensional model

Rare temperature histories and cirrus ice number density in a parcel and a one-dimensional model

Atmospheric Chemistry and Physics, 14, 13013-13022, 2014

Author(s): D. M. Murphy

A parcel and a one-dimensional model are used to investigate the temperature dependence of ice crystal number density. The number of ice crystals initially formed in a cold cirrus cloud is very sensitive to the nucleation mechanism and the detailed history of cooling rates during nucleation. A possible small spread in the homogeneous freezing threshold due to varying particle composition is identified as a sensitive nucleation parameter. In a parcel model, the slow growth rate of ice crystals at low temperatures inherently leads to a strong increase in ice number density at low temperatures. This temperature dependence is not observed. The model temperature dependence occurs for a wide range of assumptions and for either homogeneous or, less strongly, heterogeneous freezing. However, the parcel model also shows that random temperature fluctuations result in an extremely wide range of ice number densities. A one-dimensional model is used to show that the rare temperature trajectories resulting in the lowest number densities are disproportionately important. Low number density ice crystals sediment and influence a large volume of air. When such fall streaks are included, the ice number becomes less sensitive to the details of nucleation than it is in a parcel model. The one-dimensional simulations have a more realistic temperature dependence than the parcel mode. The one-dimensional model also produces layers with vertical dimensions of meters even if the temperature forcing has a much broader vertical wavelength. Unlike warm clouds, cirrus clouds are frequently surrounded by supersaturated air. Sedimentation through supersaturated air increases the importance of any process that produces small numbers of ice crystals. This paper emphasizes the relatively rare temperature trajectories that produce the fewest crystals. Other processes are heterogeneous nucleation, sedimentation from the very bottom of clouds, annealing of disordered to hexagonal ice, and entrainment.

Posted on 9 December 2014 | 12:00 am


Megacity emission plume characteristics in summer and winter investigated by mobile aerosol and trace gas measurements: the Paris metropolitan area

Megacity emission plume characteristics in summer and winter investigated by mobile aerosol and trace gas measurements: the Paris metropolitan area

Atmospheric Chemistry and Physics, 14, 12931-12950, 2014

Author(s): S.-L. von der Weiden-Reinmüller, F. Drewnick, Q. J. Zhang, F. Freutel, M. Beekmann, and S. Borrmann

For the investigation of megacity emission plume characteristics mobile aerosol and trace gas measurements were carried out in the greater Paris region in July 2009 and January–February 2010 within the EU FP7 MEGAPOLI project (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation). The deployed instruments measured physical and chemical properties of sub-micron aerosol particles, gas phase constituents of relevance for urban air pollution studies and meteorological parameters. The emission plume was identified based on fresh pollutant (e.g., particle-bound polycyclic aromatic hydrocarbons, black carbon, CO2 and NOx) concentration changes in combination with wind direction data. The classification into megacity influenced and background air masses allowed a characterization of the emission plume during summer and winter environmental conditions. On average, a clear increase of fresh pollutant concentrations in plume compared to background air masses was found for both seasons. For example, an average increase of 190% (+ 8.8 ng m−3) in summer and of 130% (+ 18.1 ng m−3) in winter was found for particle-bound polycyclic aromatic hydrocarbons in plume air masses. The aerosol particle size distribution in plume air masses was influenced by nucleation and growth due to coagulation and condensation in summer, while in winter only the latter process (i.e., particle growth) seemed to be initiated by urban pollution. The observed distribution of fresh pollutants in the emission plume – its cross sectional Gaussian-like profile and the exponential decrease of pollutant concentrations with increasing distance to the megacity – are in agreement with model results. Differences between model and measurements were found for plume center location, plume width and axial plume extent. In general, dilution was identified as the dominant process determining the axial variations within the Paris emission plume. For in-depth analysis of transformation processes occurring in the advected plume, simultaneous measurements at a suburban measurement site and a stationary site outside the metropolitan area using the mobile laboratory have proven to be most useful. Organic aerosol oxidation was observed in summer, while in winter transformation processes seemed to occur at a slower rate.

Posted on 8 December 2014 | 12:00 am


Stratospheric ozone depletion from future nitrous oxide increases

Stratospheric ozone depletion from future nitrous oxide increases

Atmospheric Chemistry and Physics, 14, 12967-12982, 2014

Author(s): W. Wang, W. Tian, S. Dhomse, F. Xie, J. Shu, and J. Austin

We have investigated the impact of the assumed nitrous oxide (N2O) increases on stratospheric chemistry and dynamics using a series of idealized simulations with a coupled chemistry-climate model (CCM). In a future cooler stratosphere the net yield of NOy from N2O is shown to decrease in a reference run following the IPCC A1B scenario, but NOy can still be significantly increased by extra increases of N2O over 2001–2050. Over the last decade of simulations, 50% increases in N2O result in a maximal 6% reduction in ozone mixing ratios in the middle stratosphere at around 10 hPa and an average 2% decrease in the total ozone column (TCO) compared with the control run. This enhanced destruction could cause an ozone decline in the first half of this century in the middle stratosphere around 10 hPa, while global TCO still shows an increase at the same time. The results from a multiple linear regression analysis and sensitivity simulations with different forcings show that the chemical effect of N2O increases dominates the N2O-induced ozone depletion in the stratosphere, while the dynamical and radiative effects of N2O increases are overall insignificant. The analysis of the results reveals that the ozone depleting potential of N2O varies with the time period and is influenced by the environmental conditions. For example, carbon dioxide (CO2) increases can strongly offset the ozone depletion effect of N2O.

Posted on 8 December 2014 | 12:00 am


Estimating regional fluxes of CO2 and CH4 using space-borne observations of XCH4: XCO2

Estimating regional fluxes of CO2 and CH4 using space-borne observations of XCH4: XCO2

Atmospheric Chemistry and Physics, 14, 12883-12895, 2014

Author(s): A. Fraser, P. I. Palmer, L. Feng, H. Bösch, R. Parker, E. J. Dlugokencky, P. B. Krummel, and R. L. Langenfelds

We use the GEOS-Chem global 3-D atmospheric chemistry transport model to interpret XCH4:XCO2 column ratios retrieved from the Japanese Greenhouse Gases Observing Satellite (GOSAT). The advantage of these data over CO2 and CH4 columns retrieved independently using a full physics optimal estimation algorithm is that they are less prone to scattering-related regional biases. We show that the model is able to reproduce observed global and regional spatial (mean bias =0.7%) and temporal variations (global r2=0.92) of this ratio with a model bias < 2.5%. We also show that these variations are driven by emissions of CO2 and CH4 that are typically 6 months out of phase, which may reduce the sensitivity of the ratio to changes in either gas. To simultaneously estimate fluxes of CO2 and CH4 we use a maximum likelihood estimation approach. We use two approaches to resolve independent flux estimates of these two gases using GOSAT observations of XCH4:XCO2: (1) the a priori error covariance between CO2 and CH4 describing common source from biomass burning; and (2) also fitting independent surface atmospheric measurements of CH4 and CO2 mole fraction that provide additional constraints, improving the effectiveness of the observed GOSAT ratio to constrain flux estimates. We demonstrate the impact of these two approaches using numerical experiments. A posteriori flux estimates inferred using only the GOSAT ratios and taking advantage of the error covariance due to biomass burning are not consistent with the true fluxes in our experiments, as the inversion system cannot judge which species' fluxes to adjust. This reflects the weak dependence of XCH4:XCO2 on biomass burning. We find that adding the surface data effectively provides an "anchor" to the inversion that dramatically improves the ability of the GOSAT ratios to infer both CH4 and CO2 fluxes. We show that the regional flux estimates inferred from GOSAT XCH4:XCO2 ratios together with the surface mole fraction data during 2010 are typically consistent with or better than the corresponding values inferred from fitting XCH4 or the full-physics XCO2 data products, as judged by a posteriori uncertainties. We show that the fluxes inferred from the ratio measurements perform best over regions where there is a large seasonal cycle such as Tropical South America, for which we report a small but significant annual source of CO2 compared to a small annual sink inferred from the XCO2 data. We argue that given that the ratio measurements are less compromised by systematic error than the full physics data products, the resulting a~posteriori estimates and uncertainties provide a more faithful description of the truth. Based on our analysis we also argue that by using the ratios we may be reaching the current limits on the precision of these observed space-based data.

Posted on 8 December 2014 | 12:00 am


Effect of different emission inventories on modeled ozone and carbon monoxide in Southeast Asia

Effect of different emission inventories on modeled ozone and carbon monoxide in Southeast Asia

Atmospheric Chemistry and Physics, 14, 12983-13012, 2014

Author(s): T. Amnuaylojaroen, M. C. Barth, L. K. Emmons, G. R. Carmichael, J. Kreasuwun, S. Prasitwattanaseree, and S. Chantara

In order to improve our understanding of air quality in Southeast Asia, the anthropogenic emissions inventory must be well represented. In this work, we apply different anthropogenic emission inventories in the Weather Research and Forecasting Model with Chemistry (WRF-Chem) version 3.3 using Model for Ozone and Related Chemical Tracers (MOZART) gas-phase chemistry and Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) aerosols to examine the differences in predicted carbon monoxide (CO) and ozone (O3) surface mixing ratios for Southeast Asia in March and December 2008. The anthropogenic emission inventories include the Reanalysis of the TROpospheric chemical composition (RETRO), the Intercontinental Chemical Transport Experiment-Phase B (INTEX-B), the MACCity emissions (adapted from the Monitoring Atmospheric Composition and Climate and megacity Zoom for the Environment projects), the Southeast Asia Composition, Cloud, Climate Coupling Regional Study (SEAC4RS) emissions, and a combination of MACCity and SEAC4RS emissions. Biomass-burning emissions are from the Fire Inventory from the National Center for Atmospheric Research (NCAR) (FINNv1) model. WRF-Chem reasonably predicts the 2 m temperature, 10 m wind, and precipitation. In general, surface CO is underpredicted by WRF-Chem while surface O3 is overpredicted. The NO2 tropospheric column predicted by WRF-Chem has the same magnitude as observations, but tends to underpredict the NO2 column over the equatorial ocean and near Indonesia. Simulations using different anthropogenic emissions produce only a slight variability of O3 and CO mixing ratios, while biomass-burning emissions add more variability. The different anthropogenic emissions differ by up to 30% in CO emissions, but O3 and CO mixing ratios averaged over the land areas of the model domain differ by ~4.5% and ~8%, respectively, among the simulations. Biomass-burning emissions create a substantial increase for both O3 and CO by ~29% and ~16%, respectively, when comparing the March biomass-burning period to the December period with low biomass-burning emissions. The simulations show that none of the anthropogenic emission inventories are better than the others for predicting O3 surface mixing ratios. However, the simulations with different anthropogenic emission inventories do differ in their predictions of CO surface mixing ratios producing variations of ~30% for March and 10–20% for December at Thai surface monitoring sites.

Posted on 8 December 2014 | 12:00 am


Reactive oxygen species associated with water-soluble PM2.5 in the southeastern United States: spatiotemporal trends and source apportionment

Reactive oxygen species associated with water-soluble PM2.5 in the southeastern United States: spatiotemporal trends and source apportionment

Atmospheric Chemistry and Physics, 14, 12915-12930, 2014

Author(s): V. Verma, T. Fang, H. Guo, L. King, J. T. Bates, R. E. Peltier, E. Edgerton, A. G. Russell, and R. J. Weber

We assess the potential of the water-soluble fraction of atmospheric fine aerosols in the southeastern United States to generate reactive oxygen species (ROS) and identify major ROS-associated emission sources. ROS-generation potential of particles was quantified by the dithiothreitol (DTT) assay and involved analysis of fine particulate matter (PM) extracted from high-volume quartz filters (23 h integrated samples) collected at various sites in different environmental settings in the southeast, including three urban-Atlanta sites, in addition to a rural site. Paired sampling was conducted with one fixed site in Atlanta (Jefferson Street), representative of the urban environment, with the others rotating among different sites, for ~250 days between June 2012 and September 2013 (N=483). A simple linear regression between the DTT activity and aerosol chemical components revealed strong associations between PM ROS-generation potential and secondary organic aerosol (WSOC – water-soluble organic carbon) in summer, and biomass burning markers in winter. Redox-active metals were also somewhat correlated with the DTT activity, but mostly at urban and roadside sites. Positive matrix factorization (PMF) was applied to apportion the relative contribution of various sources to the ROS-generation potential of water-soluble PM2.5 in urban Atlanta. PMF showed that vehicular emissions contribute uniformly throughout the year (12–25%), while secondary oxidation processes dominated the DTT activity in summer (46%) and biomass burning in winter (47%). Road dust was significant only during drier periods (~12% in summer and fall). Source apportionment by chemical mass balance (CMB) was reasonably consistent with PMF, but with higher contribution from vehicular emissions (32%). Given the spatially large data set of PM sampled over an extended period, the study reconciles the results from previous work that showed only region- or season-specific aerosol components or sources contributing to PM ROS activity, possibly due to smaller sample sizes. The ubiquitous nature of the major sources of PM-associated ROS suggests widespread population exposures to aerosol components that have the ability to catalyze the production of oxidants in vivo.

Posted on 8 December 2014 | 12:00 am


Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide

Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide

Atmospheric Chemistry and Physics, 14, 12951-12964, 2014

Author(s): A. W. Birdsall, C. R. Miner, L. E. Mael, and M. J. Elrod

Recently, methacrylic acid epoxide (MAE) has been proposed as a precursor to an important class of isoprene-derived compounds found in secondary organic aerosol (SOA): 2-methylglyceric acid (2-MG) and a set of oligomers, nitric acid esters, and sulfuric acid esters related to 2-MG. However, the specific chemical mechanisms by which MAE could form these compounds have not been previously studied with experimental methods. In order to determine the relevance of these processes to atmospheric aerosol, MAE and 2-MG have been synthesized and a series of bulk solution-phase experiments aimed at studying the reactivity of MAE using nuclear magnetic resonance (NMR) spectroscopy have been performed. The present results indicate that the acid-catalyzed MAE reaction is more than 600 times slower than a similar reaction of an important isoprene-derived epoxide, but is still expected to be kinetically feasible in the atmosphere on more acidic SOA. The specific mechanism by which MAE leads to oligomers was identified, and the reactions of MAE with a number of atmospherically relevant nucleophiles were also investigated. Because the nucleophilic strengths of water, sulfate, alcohols (including 2-MG), and acids (including MAE and 2-MG) in their reactions with MAE were found to be of similar magnitudes, it is expected that a diverse variety of MAE + nucleophile product species may be formed on ambient SOA. Thus, the results indicate that epoxide chain reaction oligomerization will be limited by the presence of high concentrations of non-epoxide nucleophiles (such as water); this finding is consistent with previous environmental chamber investigations of the relative humidity dependence of 2-MG-derived oligomerization processes and suggests that extensive oligomerization may not be likely on ambient SOA because of other competitive MAE reaction mechanisms.

Posted on 8 December 2014 | 12:00 am


A regional CO2 observing system simulation experiment for the ASCENDS satellite mission

A regional CO2 observing system simulation experiment for the ASCENDS satellite mission

Atmospheric Chemistry and Physics, 14, 12897-12914, 2014

Author(s): J. S. Wang, S. R. Kawa, J. Eluszkiewicz, D. F. Baker, M. Mountain, J. Henderson, T. Nehrkorn, and T. S. Zaccheo

Top–down estimates of the spatiotemporal variations in emissions and uptake of CO2 will benefit from the increasing measurement density brought by recent and future additions to the suite of in situ and remote CO2 measurement platforms. In particular, the planned NASA Active Sensing of CO2 Emissions over Nights, Days, and Seasons (ASCENDS) satellite mission will provide greater coverage in cloudy regions, at high latitudes, and at night than passive satellite systems, as well as high precision and accuracy. In a novel approach to quantifying the ability of satellite column measurements to constrain CO2 fluxes, we use a portable library of footprints (surface influence functions) generated by the Stochastic Time-Inverted Lagrangian Transport (STILT) model in combination with the Weather Research and Forecasting (WRF) model in a regional Bayesian synthesis inversion. The regional Lagrangian particle dispersion model framework is well suited to make use of ASCENDS observations to constrain weekly fluxes in North America at a high resolution, in this case at 1° latitude × 1° longitude. We consider random measurement errors only, modeled as a function of the mission and instrument design specifications along with realistic atmospheric and surface conditions. We find that the ASCENDS observations could potentially reduce flux uncertainties substantially at biome and finer scales. At the grid scale and weekly resolution, the largest uncertainty reductions, on the order of 50%, occur where and when there is good coverage by observations with low measurement errors and the a priori uncertainties are large. Uncertainty reductions are smaller for a 1.57 ?m candidate wavelength than for a 2.05 ?m wavelength, and are smaller for the higher of the two measurement error levels that we consider (1.0 ppm vs. 0.5 ppm clear-sky error at Railroad Valley, Nevada). Uncertainty reductions at the annual biome scale range from ~40% to ~75% across our four instrument design cases and from ~65% to ~85% for the continent as a whole. Tests suggest that the quantitative results are moderately sensitive to assumptions regarding a priori uncertainties and boundary conditions. The a posteriori flux uncertainties we obtain, ranging from 0.01 to 0.06 Pg C yr?1 across the biomes, would meet requirements for improved understanding of long-term carbon sinks suggested by a previous study.

Posted on 8 December 2014 | 12:00 am


The use of SMILES data to study ozone loss in the Arctic winter 2009/2010 and comparison with Odin/SMR data using assimilation techniques

The use of SMILES data to study ozone loss in the Arctic winter 2009/2010 and comparison with Odin/SMR data using assimilation techniques

Atmospheric Chemistry and Physics, 14, 12855-12869, 2014

Author(s): K. Sagi, D. Murtagh, J. Urban, H. Sagawa, and Y. Kasai

The Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) on board the International Space Station observed ozone in the stratosphere with high precision from October 2009 to April 2010. Although SMILES measurements only cover latitudes from 38° S to 65° N, the combination of data assimilation methods and an isentropic advection model allows us to quantify the ozone depletion in the 2009/2010 Arctic polar winter by making use of the instability of the polar vortex in the northern hemisphere. Ozone data from both SMILES and Odin/SMR (Sub-Millimetre Radiometer) for the winter were assimilated into the Dynamical Isentropic Assimilation Model for OdiN Data (DIAMOND). DIAMOND is an off-line wind-driven transport model on isentropic surfaces. Wind data from the operational analyses of the European Centre for Medium- Range Weather Forecasts (ECMWF) were used to drive the model. In this study, particular attention is paid to the cross isentropic transport of the tracer in order to accurately assess the ozone loss. The assimilated SMILES ozone fields agree well with the limitation of noise induced variability within the SMR fields despite the limited latitude coverage of the SMILES observations. Ozone depletion has been derived by comparing the ozone field acquired by sequential assimilation with a passively transported ozone field initialized on 1 December 2009. Significant ozone loss was found in different periods and altitudes from using both SMILES and SMR data: The initial depletion occurred at the end of January below 550 K with an accumulated loss of 0.6–1.0 ppmv (approximately 20%) by 1 April. The ensuing loss started from the end of February between 575 K and 650 K. Our estimation shows that 0.8–1.3 ppmv (20–25 %) of O3 has been removed at the 600 K isentropic level by 1 April in volume mixing ratio (VMR).

Posted on 8 December 2014 | 12:00 am


Atmospheric measurements of ratios between CO2 and co-emitted species from traffic: a tunnel study in the Paris megacity

Atmospheric measurements of ratios between CO2 and co-emitted species from traffic: a tunnel study in the Paris megacity

Atmospheric Chemistry and Physics, 14, 12871-12882, 2014

Author(s): L. Ammoura, I. Xueref-Remy, V. Gros, A. Baudic, B. Bonsang, J.-E. Petit, O. Perrussel, N. Bonnaire, J. Sciare, and F. Chevallier

Measurements of CO2, CO, NOx and selected Volatile Organic Compounds (VOCs) mole fractions were performed continuously during a 10-day period in the Guy Môquet tunnel in Thiais, a peri-urban area about 15 km south of the centre of Paris, between 28 September and 8 October 2012. This data set is used here to identify the characteristics of traffic-emitted CO2 by evaluating its ratios to co-emitted species for the first time in the Paris region. High coefficients of determination (r2 > 0.7) are observed between CO2 and certain compounds that are characteristic of the traffic source (CO, NOx, benzene, xylenes and acetylene). Weak correlations (r2 < 0.2) are found with species such as propane, n-butane and i-butane that are associated with fuel evaporation, an insignificant source for CO2. To better characterise the traffic signal we focus only on species that are well-correlated with CO2 and on rush-hour periods characterised by the highest traffic-related mole fractions. From those mole fractions we remove the nighttime-average weekday mole fraction obtained for each species that we infer to be the most appropriate background signal for our study. Then we calculate observed ?species / ?CO2 ratios, which we compare with the ones provided by the 2010 bottom–up high-resolved regional emission inventory from Airparif (the association in charge of monitoring the air quality in Île-de-France), focusing on local emission data for the specific road of the tunnel. We find an excellent agreement (2%) between the local inventory emission CO / CO2 ratio and our observed ?CO / ?CO2 ratio. Former tunnel experiments carried out elsewhere in the world provided observed ?CO / ?CO2 ratios that differ from 49 to 592% to ours. This variability can be related to technological improvement of vehicles, differences in driving conditions, and fleet composition. We also find a satisfactory agreement with the Airparif inventory for n-propylbenzene, n-pentane and xylenes to CO2 ratios. For most of the other species, the ratios obtained from the local emission inventory overestimate the observed ratios to CO2 by 34 to more than 300%. However, the emission ratios of NOx, o-xylene and i-pentane are underestimated by 30 to 79%. One main cause of such high differences between the inventory and our observations is likely the obsolete feature of the VOCs speciation matrix of the inventory that has not been updated since 1998, although law regulations on some VOCs have occurred since that time. Our study bears important consequences, discussed in the conclusion, for the characterisation of the urban CO2 plume and for atmospheric inverse modelling of urban CO2 emissions.

Posted on 8 December 2014 | 12:00 am


Henry's law constants of polyols

Henry's law constants of polyols

Atmospheric Chemistry and Physics, 14, 12815-12837, 2014

Author(s): S. Compernolle and J.-F. Müller

Henry's law constants (HLC) are derived for several polyols bearing between 2 and 6 hydroxyl groups, based on literature data for water activity, vapour pressure and/or solubility. While deriving HLC and depending on the case, also infinite dilution activity coefficients (IDACs), solid state vapour pressures or activity coefficient ratios are obtained as intermediate results. An error analysis on the intermediate quantities and the obtained HLC is included. For most compounds, these are the first values reported, while others compare favourably with literature data in most cases. Using these values and those from a previous work (Compernolle and Müller, 2014), an assessment is made on the partitioning of polyols, diacids and hydroxy acids to droplet and aqueous aerosol.

Posted on 8 December 2014 | 12:00 am


Nitrous oxide emissions from a commercial cornfield (Zea mays) measured using the eddy covariance technique

Nitrous oxide emissions from a commercial cornfield (Zea mays) measured using the eddy covariance technique

Atmospheric Chemistry and Physics, 14, 12839-12854, 2014

Author(s): H. Huang, J. Wang, D. Hui, D. R. Miller, S. Bhattarai, S. Dennis, D. Smart, T. Sammis, and K. C. Reddy

Increases in observed atmospheric concentrations of the long-lived greenhouse gas nitrous oxide (N2O) have been well documented. However, information on event-related instantaneous emissions during fertilizer applications is lacking. With the development of fast-response N2O analyzers, the eddy covariance (EC) technique can be used to gather instantaneous measurements of N2O concentrations to quantify the exchange of nitrogen between the soil and atmosphere. The objectives of this study were to evaluate the performance of a new EC system, to measure the N2O flux with the system, and finally to examine relationships of the N2O flux with soil temperature, soil moisture, precipitation, and fertilization events. An EC system was assembled with a sonic anemometer and a fast-response N2O analyzer (quantum cascade laser spectrometer) and applied in a cornfield in Nolensville, Tennessee during the 2012 corn growing season (4 April–8 August). Fertilizer amounts totaling 217 kg N ha?1 were applied to the experimental site. Results showed that this N2O EC system provided reliable N2O flux measurements. The cumulative emitted N2O amount for the entire growing season was 6.87 kg N2O-N ha?1. Seasonal fluxes were highly dependent on soil moisture rather than soil temperature. This study was one of the few experiments that continuously measured instantaneous, high-frequency N2O emissions in crop fields over a growing season of more than 100 days.

Posted on 8 December 2014 | 12:00 am


Corrigendum to "Air-sea exchange and gas-particle partitioning of polycyclic aromatic hydrocarbons in the Mediterranean" published in Atmos. Chem. Phys., 14, 8905–8915, 2014

Corrigendum to "Air-sea exchange and gas-particle partitioning of polycyclic aromatic hydrocarbons in the Mediterranean" published in Atmos. Chem. Phys., 14, 8905–8915, 2014

Atmospheric Chemistry and Physics, 14, 12965-12965, 2014

Author(s): M. D. Mulder, A. Heil, P. Kuku?ka, J. Klánová, J. Kuta, R. Prokeš, F. Sprovieri, and G. Lammel

No abstract available.

Posted on 8 December 2014 | 12:00 am


On the hiatus in the acceleration of tropical upwelling since the beginning of the 21st century

On the hiatus in the acceleration of tropical upwelling since the beginning of the 21st century

Atmospheric Chemistry and Physics, 14, 12803-12814, 2014

Author(s): J. Aschmann, J. P. Burrows, C. Gebhardt, A. Rozanov, R. Hommel, M. Weber, and A. M. Thompson

Chemistry–climate models predict an acceleration of the upwelling branch of the Brewer–Dobson circulation as a consequence of increasing global surface temperatures, resulting from elevated levels of atmospheric greenhouse gases. The observed decrease of ozone in the tropical lower stratosphere during the last decades of the 20th century is consistent with the anticipated acceleration of upwelling. However, more recent satellite observations of ozone reveal that this decrease has unexpectedly stopped in the first decade of the 21st century, challenging the implicit assumption of a continuous acceleration of tropical upwelling. In this study we use three decades of chemistry-transport-model simulations (1980–2013) to investigate this phenomenon and resolve this apparent contradiction. Aside from a high-bias between 1985–1990, our model is able to reproduce the observed tropical lower stratosphere ozone record. A regression analysis identifies a significant decrease in the early period followed by a statistically robust trend-change after 2002, in qualitative agreement with the observations. We demonstrate that this trend-change is correlated with structural changes in the vertical transport, represented in the model by diabatic heating rates taken from the reanalysis product Era-Interim. These changes lead to a hiatus in the acceleration of tropical upwelling between 70–30 hPa and a southward shift of the tropical pipe at 30 and 100 hPa during the past decade, which appear to be the primary causes for the observed trend-change in ozone.

Posted on 5 December 2014 | 12:00 am


Emissions of biogenic volatile organic compounds and subsequent photochemical production of secondary organic aerosol in mesocosm studies of temperate and tropical plant species

Emissions of biogenic volatile organic compounds and subsequent photochemical production of secondary organic aerosol in mesocosm studies of temperate and tropical plant species

Atmospheric Chemistry and Physics, 14, 12781-12801, 2014

Author(s): K. P. Wyche, A. C. Ryan, C. N. Hewitt, M. R. Alfarra, G. McFiggans, T. Carr, P. S. Monks, K. L. Smallbone, G. Capes, J. F. Hamilton, T. A. M. Pugh, and A. R. MacKenzie

Silver birch (Betula pendula) and three Southeast Asian tropical plant species (Ficus cyathistipula, Ficus benjamina and Caryota millis) from the pantropical fig and palm genera were grown in a purpose-built and environment-controlled whole-tree chamber. The volatile organic compounds emitted from these trees were characterised and fed into a linked photochemical reaction chamber where they underwent photo-oxidation under a range of controlled conditions (relative humidity or RH ~65–89%, volatile organic compound-to-NOx or VOC / NOx ~3–9 and NOx ~2 ppbV). Both the gas phase and the aerosol phase of the reaction chamber were monitored in detail using a comprehensive suite of on-line and off-line chemical and physical measurement techniques.

Silver birch was found to be a high monoterpene and sesquiterpene but low isoprene emitter, and its emissions were observed to produce measurable amounts of secondary organic aerosol (SOA) via both nucleation and condensation onto pre-existing seed aerosol (YSOA 26–39%). In contrast, all three tropical species were found to be high isoprene emitters with trace emissions of monoterpenes and sesquiterpenes. In tropical plant experiments without seed aerosol there was no measurable SOA nucleation, but aerosol mass was shown to increase when seed aerosol was present. Although principally isoprene emitting, the aerosol mass produced from tropical fig was mostly consistent (i.e. in 78 out of 120 aerosol mass calculations using plausible parameter sets of various precursor specific yields) with condensation of photo-oxidation products of the minor volatile organic compounds (VOCs) co-emitted; no significant aerosol yield from condensation of isoprene oxidation products was required in the interpretations of the experimental results. This finding is in line with previous reports of organic aerosol loadings consistent with production from minor biogenic VOCs co-emitted with isoprene in principally isoprene-emitting landscapes in Southeast Asia. Moreover, in general the amount of aerosol mass produced from the emissions of the principally isoprene-emitting plants was less than would be expected from published single-VOC experiments, if co-emitted species were solely responsible for the final SOA mass. Interpretation of the results obtained from the fig data sets leaves room for a potential role for isoprene in inhibiting SOA formation under certain ambient atmospheric conditions, although instrumental and experimental constraints impose a level of caution in the interpretation of the results.

Concomitant gas- and aerosol-phase composition measurements also provide a detailed overview of numerous key oxidation mechanisms at work within the systems studied, and their combined analysis provides insight into the nature of the SOA formed.

Posted on 5 December 2014 | 12:00 am


Surface-to-mountaintop transport characterised by radon observations at the Jungfraujoch

Surface-to-mountaintop transport characterised by radon observations at the Jungfraujoch

Atmospheric Chemistry and Physics, 14, 12763-12779, 2014

Author(s): A. D. Griffiths, F. Conen, E. Weingartner, L. Zimmermann, S. D. Chambers, A. G. Williams, and M. Steinbacher

Atmospheric composition measurements at Jungfraujoch are affected intermittently by boundary-layer air which is brought to the station by processes including thermally driven (anabatic) mountain winds. Using observations of radon-222, and a new objective analysis method, we quantify the land-surface influence at Jungfraujoch hour by hour and detect the presence of anabatic winds on a daily basis. During 2010–2011, anabatic winds occurred on 40% of days, but only from April to September. Anabatic wind days were associated with warmer air temperatures over a large fraction of Europe and with a shift in air-mass properties, even when comparing days with a similar mean radon concentration. Excluding days with anabatic winds, however, did not lead to a better definition of the unperturbed aerosol background than a definition based on radon alone. This implies that a radon threshold reliably excludes local influences from both anabatic and non-anabatic vertical-transport processes.

Posted on 5 December 2014 | 12:00 am


Fast transport from Southeast Asia boundary layer sources to northern Europe: rapid uplift in typhoons and eastward eddy shedding of the Asian monsoon anticyclone

Fast transport from Southeast Asia boundary layer sources to northern Europe: rapid uplift in typhoons and eastward eddy shedding of the Asian monsoon anticyclone

Atmospheric Chemistry and Physics, 14, 12745-12762, 2014

Author(s): B. Vogel, G. Günther, R. Müller, J.-U. Grooß, P. Hoor, M. Krämer, S. Müller, A. Zahn, and M. Riese

Enhanced tropospheric trace gases such as CO, CH4 and H2O and reduced stratospheric O3 were measured in situ in the lowermost stratosphere over northern Europe on 26 September 2012 during the TACTS aircraft campaign. The measurements indicate that these air masses clearly differ from the stratospheric background. The calculation of 40-day backward trajectories with the trajectory module of the CLaMS model shows that these air masses are affected by the Asian monsoon anticyclone. Some air masses originate from the boundary layer in Southeast Asia/West Pacific and are rapidly lifted (1–2 days) within a typhoon up to the outer edge of the Asian monsoon anticyclone. Afterwards, the air parcels are entrained by the anticyclonic circulation of the Asian monsoon. The subsequent long-range transport (8–14 days) of enhanced water vapour and pollutants to the lowermost stratosphere in northern Europe is driven by eastward transport of tropospheric air from the Asian monsoon anticyclone caused by an eddy shedding event. We found that the combination of rapid uplift by a typhoon and eastward eddy shedding from the Asian monsoon anticyclone is a novel fast transport pathway that may carry boundary emissions from Southeast Asia/West Pacific within approximately 5 weeks to the lowermost stratosphere in northern Europe.

Posted on 4 December 2014 | 12:00 am


Trends in peroxyacetyl nitrate (PAN) in the upper troposphere and lower stratosphere over southern Asia during the summer monsoon season: regional impacts

Trends in peroxyacetyl nitrate (PAN) in the upper troposphere and lower stratosphere over southern Asia during the summer monsoon season: regional impacts

Atmospheric Chemistry and Physics, 14, 12725-12743, 2014

Author(s): S. Fadnavis, M. G. Schultz, K. Semeniuk, A. S. Mahajan, L. Pozzoli, S. Sonbawne, S. D. Ghude, M. Kiefer, and E. Eckert

We analyze temporal trends of peroxyacetyl nitrate (PAN) retrievals from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) during 2002–2011 in the altitude range 8–23 km over the Asian summer monsoon (ASM) region. The greatest enhancements of PAN mixing ratios in the upper troposphere and lower stratosphere (UTLS) are seen during the summer monsoon season from June to September. During the monsoon season, the mole fractions of PAN show statistically significant (at 2?) positive trends from 0.2 ± 0.05 to 4.6 ± 3.1 ppt yr?1 (except between 12 and 14 km) which is higher than the annual mean trends of 0.1 ± 0.05 to 2.7 ± 0.8 ppt yr?1. These rising concentrations point to increasing NOx (= NO + NO2) and volatile organic compound (VOC) emissions from developing nations in Asia, notably India and China.

We analyze the influence of monsoon convection on the distribution of PAN in UTLS with simulations using the global chemistry–climate model ECHAM5-HAMMOZ. During the monsoon, transport into the UTLS over the Asian region primarily occurs from two convective zones, one the South China Sea and the other over the southern flank of the Himalayas.

India and China host NOx-limited regimes for ozone photochemical production, and thus we use the model to evaluate the contributions from enhanced NOx emissions to the changes in PAN, HNO3 and O3 concentrations in the UTLS. From a set of sensitivity experiments with emission changes in particular regions, it can be concluded that Chinese emissions have a greater impact on the concentrations of these species than Indian emissions. According to SCanning Imaging Absorption SpectroMeter for Atmospheric CHartographY (SCIAMACHY) NO2 retrievals NOx emissions increases over India have been about half of those over China between 2002 and 2011.

Posted on 4 December 2014 | 12:00 am


Potential climate forcing of land use and land cover change

Potential climate forcing of land use and land cover change

Atmospheric Chemistry and Physics, 14, 12701-12724, 2014

Author(s): D. S. Ward, N. M. Mahowald, and S. Kloster

Pressure on land resources is expected to increase as global population continues to climb and the world becomes more affluent, swelling the demand for food. Changing climate may exert additional pressures on natural lands as present-day productive regions may shift, or soil quality may degrade, and the recent rise in demand for biofuels increases competition with edible crops for arable land. Given these projected trends there is a need to understand the global climate impacts of land use and land cover change (LULCC). Here we quantify the climate impacts of global LULCC in terms of modifications to the balance between incoming and outgoing radiation at the top of the atmosphere (radiative forcing, RF) that are caused by changes in long-lived and short-lived greenhouse gas concentrations, aerosol effects, and land surface albedo. We attribute historical changes in terrestrial carbon storage, global fire emissions, secondary organic aerosol emissions, and surface albedo to LULCC using simulations with the Community Land Model version 3.5. These LULCC emissions are combined with estimates of agricultural emissions of important trace gases and mineral dust in two sets of Community Atmosphere Model simulations to calculate the RF of changes in atmospheric chemistry and aerosol concentrations attributed to LULCC. With all forcing agents considered together, we show that 40% (±16%) of the present-day anthropogenic RF can be attributed to LULCC. Changes in the emission of non-CO2 greenhouse gases and aerosols from LULCC enhance the total LULCC RF by a factor of 2 to 3 with respect to the LULCC RF from CO2 alone. This enhancement factor also applies to projected LULCC RF, which we compute for four future scenarios associated with the Representative Concentration Pathways. We attribute total RFs between 0.9 and 1.9 W m?2 to LULCC for the year 2100 (relative to a pre-industrial state). To place an upper bound on the potential of LULCC to alter the global radiation budget, we include a fifth scenario in which all arable land is cultivated by 2100. This theoretical extreme case leads to a LULCC RF of 3.9 W m?2 (±0.9 W m?2), suggesting that not only energy policy but also land policy is necessary to minimize future increases in RF and associated climate changes.

Posted on 3 December 2014 | 12:00 am


Tropospheric carbon monoxide over the Pacific during HIPPO: two-way coupled simulation of GEOS-Chem and its multiple nested models

Tropospheric carbon monoxide over the Pacific during HIPPO: two-way coupled simulation of GEOS-Chem and its multiple nested models

Atmospheric Chemistry and Physics, 14, 12649-12663, 2014

Author(s): Y.-Y. Yan, J.-T. Lin, Y. Kuang, D. Yang, and L. Zhang

Global chemical transport models (CTMs) are used extensively to study air pollution and transport at a global scale. These models are limited by coarse horizontal resolutions that do not allow for a detailed representation of small-scale nonlinear processes over the pollutant source regions. Here we couple the global GEOS-Chem CTM and its three high-resolution nested models to simulate the tropospheric carbon monoxide (CO) over the Pacific Ocean during five High-performance Instrumented Airborne Platform for Environmental Research (HIAPER) Pole-to-Pole Observations (HIPPO) campaigns between 2009 and 2011. We develop a two-way coupler, the PeKing University CouPLer (PKUCPL), allowing for the exchange and interaction of chemical constituents between the global model (at 2.5° long. × 2° lat.) and the three nested models (at 0.667° long. × 0.5° lat.) covering Asia, North America, and Europe. The coupler obtains nested model results to modify the global model simulation within the respective nested domains, and simultaneously acquires global model results to provide lateral boundary conditions (LBCs) for the nested models.

Compared to the global model alone, the two-way coupled simulation results in enhanced CO concentrations in the nested domains. Sensitivity tests suggest the enhancement to be a result of improved representation of the spatial distributions of CO, nitrogen oxides, and non-methane volatile organic compounds, the meteorological dependence of natural emissions, and other resolution-dependent processes. The relatively long lifetime of CO allows for the enhancement to be accumulated and carried across the globe. We found that the two-way coupled simulation increased the global tropospheric mean CO concentrations in 2009 by 10.4%, with a greater enhancement at 13.3% in the Northern Hemisphere. Coincidently, the global tropospheric mean hydroxyl radical (OH) was reduced by 4.2%, resulting in a 4.2% enhancement in the methyl chloroform lifetime (MCF; via reaction with tropospheric OH). The resulting CO and OH contents and MCF lifetime are closer to observation-based estimates.

Both the global and the two-way coupled models capture the general spatiotemporal patterns of HIPPO CO over the Pacific. The two-way coupled simulation is much closer to HIPPO CO, with a mean bias of 1.1 ppb (1.4%) below 9 km compared to the bias at ?7.2 ppb (?9.2%) for the global model alone. The improvement is most apparent over the North Pacific. Our test simulations show that the global model alone could resemble the two-way coupled simulation (especially below 4 km) by increasing its global CO emissions by 15% for HIPPO-1 and HIPPO-3, by 25% for HIPPO-2 and HIPPO-4, and by 35% for HIPPO-5. This has important implications for using the global model alone to constrain CO emissions. Thus, the two-way coupled simulation is a significantly improved model tool for studying the global impacts of air pollutants from major anthropogenic source regions.

Posted on 2 December 2014 | 12:00 am


Using cloud ice flux to parametrise large-scale lightning

Using cloud ice flux to parametrise large-scale lightning

Atmospheric Chemistry and Physics, 14, 12665-12682, 2014

Author(s): D. L. Finney, R. M. Doherty, O. Wild, H. Huntrieser, H. C. Pumphrey, and A. M. Blyth

Lightning is an important natural source of nitrogen oxide especially in the middle and upper troposphere. Hence, it is essential to represent lightning in chemistry transport and coupled chemistry–climate models. Using ERA-Interim meteorological reanalysis data we compare the lightning flash density distributions produced using several existing lightning parametrisations, as well as a new parametrisation developed on the basis of upward cloud ice flux at 440 hPa. The use of ice flux forms a link to the non-inductive charging mechanism of thunderstorms. Spatial and temporal distributions of lightning flash density are compared to tropical and subtropical observations for 2007–2011 from the Lightning Imaging Sensor (LIS) on the Tropical Rainfall Measuring Mission (TRMM) satellite. The well-used lightning flash parametrisation based on cloud-top height has large biases but the derived annual total flash density has a better spatial correlation with the LIS observations than other existing parametrisations. A comparison of flash density simulated by the different schemes shows that the cloud-top height parametrisation has many more instances of moderate flash densities and fewer low and high extremes compared to the other parametrisations. Other studies in the literature have shown that this feature of the cloud-top height parametrisation is in contrast to lightning observations over certain regions. Our new ice flux parametrisation shows a clear improvement over all the existing parametrisations with lower root mean square errors (RMSEs) and better spatial correlations with the observations for distributions of annual total, and seasonal and interannual variations. The greatest improvement with the new parametrisation is a more realistic representation of the zonal distribution with a better balance between tropical and subtropical lightning flash estimates. The new parametrisation is appropriate for testing in chemistry transport and chemistry–climate models that use a lightning parametrisation.

Posted on 2 December 2014 | 12:00 am


Aerosol–computational fluid dynamics modeling of ultrafine and black carbon particle emission, dilution, and growth near roadways

Aerosol–computational fluid dynamics modeling of ultrafine and black carbon particle emission, dilution, and growth near roadways

Atmospheric Chemistry and Physics, 14, 12631-12648, 2014

Author(s): L. Huang, S. L. Gong, M. Gordon, J. Liggio, R. Staebler, C. A. Stroud, G. Lu, C. Mihele, J. R. Brook, and C. Q. Jia

Many studies have shown that on-road vehicle emissions are the dominant source of ultrafine particles (UFPs; diameter < 100 nm) in urban areas and near-roadway environments. In order to advance our knowledge on the complex interactions and competition among atmospheric dilution, dispersion, and dynamics of UFPs, an aerosol dynamics–computational fluid dynamics (CFD) coupled model is developed and validated against field measurements. A unique approach of applying periodic boundary conditions is proposed to model pollutant dispersion and dynamics in one unified domain from the tailpipe level to the ambient near-road environment. This approach significantly reduces the size of the computational domain, and therefore allows fast simulation of multiple scenarios. The model is validated against measured turbulent kinetic energy (TKE) and horizontal gradient of pollution concentrations perpendicular to a major highway. Through a model sensitivity analysis, the relative importance of individual aerosol dynamical processes on the total particle number concentration (N) and particle number–size distribution (PSD) near a highway is investigated. The results demonstrate that (1) coagulation has a negligible effect on N and particle growth, (2) binary homogeneous nucleation (BHN) of H2SO4–H2O is likely responsible for elevated N closest to the road, and (3) N and particle growth are very sensitive to the condensation of semi-volatile organics (SVOCs), particle dry deposition, and the interaction between these processes. The results also indicate that, without the proper treatment of the atmospheric boundary layer (i.e., its wind profile and turbulence quantities), the nucleation rate would be underestimated by a factor of 5 in the vehicle wake region due to overestimated dilution. Therefore, introducing atmospheric boundary layer (ABL) conditions to activity-based emission models may potentially improve their performance in estimating UFP traffic emissions.

Posted on 2 December 2014 | 12:00 am


Atmospheric black carbon and warming effects influenced by the source and absorption enhancement in central Europe

Atmospheric black carbon and warming effects influenced by the source and absorption enhancement in central Europe

Atmospheric Chemistry and Physics, 14, 12683-12699, 2014

Author(s): S. Nordmann, Y. F. Cheng, G. R. Carmichael, M. Yu, H. A. C. Denier van der Gon, Q. Zhang, P. E. Saide, U. Pöschl, H. Su, W. Birmili, and A. Wiedensohler

Particles containing black carbon (BC), a strong absorbing substance, exert a rather uncertain direct and indirect radiative forcing in the atmosphere. To investigate the mass concentration and absorption properties of BC particles over central Europe, the model WRF-Chem was used at a resolution of 12 km in conjunction with a high-resolution BC emission inventory (EUCAARI 42-Pan-European Carbonaceous Aerosol Inventory; 1/8° × 1/16°). The model simulation was evaluated using measurements of equivalent soot carbon, absorption coefficients and particle number concentrations at seven sites within the German Ultrafine Aerosol Network, PM mass concentrations from the dense measurement network of the German Federal Environmental Agency at 392 monitoring stations, and aerosol optical depth from MODIS and AERONET. A distinct time period (25 March to 10 April 2009) was chosen, during which the clean marine air mass prevailed in the first week and afterwards the polluted continental air mass mainly from the southeast dominated with elevated daily average BC concentration of up to 4 μ g m−3. The simulated PM mass concentration, aerosol number concentration and optical depth were in good agreement with the observations, while the modelled BC mass concentrations were found to be a factor of 2 lower than the observations. Together with back trajectories, detailed model bias analyses suggested that the current BC emission in countries to the east and south of Germany might be underestimated by a factor of 5, at least for the simulation period. Running the model with upscaled BC emissions in these regions led to a smaller model bias and a better correlation between model and measurement. In contrast, the particle absorption coefficient was positively biased by about 20% even when the BC mass concentration was underestimated by around 50%. This indicates that the internal mixture treatment of BC in the WRF-Chem optical calculation is unrealistic in our case, which overamplifies the light absorption by BC-containing particles. By adjusting the modelled mass absorption cross-section towards the measured values, the simulation of particle light absorption of BC was improved as well. Finally, the positive direct radiative forcing of BC particles at the top of the atmosphere was estimated to be in the range of 0 to +4 W m−2 over Germany for the model run with improved BC mass concentration and adjusted BC light absorption cross-section. This adjustment lowered the positive forcing of BC by up to 70%, compared with the internal mixing treatment of BC in the model simulation.

Posted on 2 December 2014 | 12:00 am


Overview and sample applications of SMILES and Odin-SMR retrievals of upper tropospheric humidity and cloud ice mass

Overview and sample applications of SMILES and Odin-SMR retrievals of upper tropospheric humidity and cloud ice mass

Atmospheric Chemistry and Physics, 14, 12613-12629, 2014

Author(s): P. Eriksson, B. Rydberg, H. Sagawa, M. S. Johnston, and Y. Kasai

Retrievals of cloud ice mass and humidity from the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) and the Odin-SMR (Sub-Millimetre Radiometer) limb sounder are presented and example applications of the data are given. SMILES data give an unprecedented view of the diurnal variation of cloud ice mass. Mean regional diurnal cycles are reported and compared to some global climate models. Some improvements in the models regarding diurnal timing and relative amplitude were noted, but the models' mean ice mass around 250 hPa is still low compared to the observations. The influence of the ENSO (El Niño–Southern Oscillation) state on the upper troposphere is demonstrated using 12 years of Odin-SMR data.

The same retrieval scheme is applied for both sensors, and gives low systematic differences between the two data sets. A special feature of this Bayesian retrieval scheme, of Monte Carlo integration type, is that values are produced for all measurements but for some atmospheric states retrieved values only reflect a priori assumptions. However, this "all-weather" capability allows a direct statistical comparison to model data, in contrast to many other satellite data sets. Another strength of the retrievals is the detailed treatment of "beam filling" that otherwise would cause large systematic biases for these passive cloud ice mass retrievals.

The main retrieval inputs are spectra around 635/525 GHz from tangent altitudes below 8/9 km for SMILES/Odin-SMR, respectively. For both sensors, the data cover the upper troposphere between 30° S and 30° N. Humidity is reported as both relative humidity and volume mixing ratio. The vertical coverage of SMILES is restricted to a single layer, while Odin-SMR gives some profiling capability between 300 and 150 hPa. Ice mass is given as the partial ice water path above 260 hPa, but for Odin-SMR ice water content, estimates are also provided. Besides a smaller contrast between most dry and wet cases, the agreement with Aura MLS (Microwave Limb Sounder) humidity data is good. In terms of tropical mean humidity, all three data sets agree within 3.5 %RHi. Mean ice mass is about a factor of 2 lower compared to CloudSat. This deviation is caused by the fact that different particle size distributions are assumed, combined with saturation and a priori influences in the SMILES and Odin-SMR data.

Posted on 1 December 2014 | 12:00 am


Chemical composition, sources, and processes of urban aerosols during summertime in northwest China: insights from high-resolution aerosol mass spectrometry

Chemical composition, sources, and processes of urban aerosols during summertime in northwest China: insights from high-resolution aerosol mass spectrometry

Atmospheric Chemistry and Physics, 14, 12593-12611, 2014

Author(s): J. Xu, Q. Zhang, M. Chen, X. Ge, J. Ren, and D. Qin

An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed along with a scanning mobility particle sizer (SMPS) and a multi-angle absorption photometer (MAAP) to measure the temporal variations of the mass loading, chemical composition, and size distribution of submicron particulate matter (PM1) in Lanzhou, northwest China, during 11 July–7 August 2012. The average (PM1 mass concentration including non-refractory (PM1 (NR-(PM1) measured by HR-ToF-AMS and black carbon (BC) measured by MAAP during this study was 24.5 ?g m?3 (ranging from 0.86 to 105 ?g m−3), with a mean composition consisting of 47% organics, 16% sulfate, 12% BC, 11% ammonium, 10% nitrate, and 4% chloride. Organic aerosol (OA) on average consisted of 70% carbon, 21% oxygen, 8% hydrogen, and 1% nitrogen, with the average oxygen-to-carbon ratio (O / C) of 0.33 and organic mass-to-carbon ratio (OM / OC) of 1.58. Positive matrix factorization (PMF) of the high-resolution organic mass spectra identified four distinct factors which represent, respectively, two primary OA (POA) emission sources (traffic and food cooking) and two secondary OA (SOA) types – a fresher, semi-volatile oxygenated OA (SV-OOA) and a more aged, low-volatility oxygenated OA (LV-OOA). Traffic-related hydrocarbon-like OA (HOA) and BC displayed distinct diurnal patterns, both with peak at ~ 07:00–11:00 (BJT: UTC +8), corresponding to the morning rush hours, while cooking-emission related OA (COA) peaked during three meal periods. The diurnal profiles of sulfate and LV-OOA displayed a broad peak between ~ 07:00 and 15:00, while those of nitrate, ammonium, and SV-OOA showed a narrower peak between ~ 08:00–13:00. The later morning and early afternoon maximum in the diurnal profiles of secondary aerosol species was likely caused by downward mixing of pollutants aloft, which were likely produced in the residual layer decoupled from the boundary layer during nighttime. The mass spectrum of SV-OOA was similar to that of coal combustion aerosol and likely influenced by coal combustion activities in Lanzhou during summer. The sources of BC were estimated by a linear decomposition algorithm that uses the time series of the NR-PM1 components. Our results indicate that a main source of BC was local traffic (47%) and that transport of regionally processed air masses also contributed significantly to BC observed in Lanzhou. Finally, the concentration and source of polycyclic aromatic hydrocarbons (PAHs) were evaluated.

Posted on 1 December 2014 | 12:00 am


The thermodynamic structure of summer Arctic stratocumulus and the dynamic coupling to the surface

The thermodynamic structure of summer Arctic stratocumulus and the dynamic coupling to the surface

Atmospheric Chemistry and Physics, 14, 12573-12592, 2014

Author(s): G. Sotiropoulou, J. Sedlar, M. Tjernström, M. D. Shupe, I. M. Brooks, and P. O. G. Persson

The vertical structure of Arctic low-level clouds and Arctic boundary layer is studied, using observations from ASCOS (Arctic Summer Cloud Ocean Study), in the central Arctic, in late summer 2008. Two general types of cloud structures are examined: the "neutrally stratified" and "stably stratified" clouds. Neutrally stratified are mixed-phase clouds where radiative-cooling near cloud top produces turbulence that generates a cloud-driven mixed layer. When this layer mixes with the surface-generated turbulence, the cloud layer is coupled to the surface, whereas when such an interaction does not occur, it remains decoupled; the latter state is most frequently observed. The decoupled clouds are usually higher compared to the coupled; differences in thickness or cloud water properties between the two cases are however not found. The surface fluxes are also very similar for both states. The decoupled clouds exhibit a bimodal thermodynamic structure, depending on the depth of the sub-cloud mixed layer (SCML): clouds with shallower SCMLs are disconnected from the surface by weak inversions, whereas those that lay over a deeper SCML are associated with stronger inversions at the decoupling height. Neutrally stratified clouds generally precipitate; the evaporation/sublimation of precipitation often enhances the decoupling state. Finally, stably stratified clouds are usually lower, geometrically and optically thinner, non-precipitating liquid-water clouds, not containing enough liquid to drive efficient mixing through cloud-top cooling.

Posted on 28 November 2014 | 12:00 am


Analysis of elevated springtime levels of Peroxyacetyl nitrate (PAN) at the high Alpine research sites Jungfraujoch and Zugspitze

Analysis of elevated springtime levels of Peroxyacetyl nitrate (PAN) at the high Alpine research sites Jungfraujoch and Zugspitze

Atmospheric Chemistry and Physics, 14, 12553-12571, 2014

Author(s): S. Pandey Deolal, S. Henne, L. Ries, S. Gilge, U. Weers, M. Steinbacher, J. Staehelin, and T. Peter

The largest atmospheric peroxyacetyl nitrate (PAN) mole fractions at remote surface sites in the Northern Hemisphere are commonly observed during the months April and May. Different formation mechanisms for this seasonal maximum have previously been suggested: hemispheric-scale production from precursors accumulated during the winter months, increased springtime transport from up-wind continents or increased regional-scale production in the atmospheric boundary layer from recent emissions. The two high Alpine research sites Jungfraujoch (Switzerland) and Zugspitze (Germany) exhibit a distinct and consistent springtime PAN maximum. Since these sites intermittently sample air masses of free-tropospheric and boundary layer origin, they are ideally suited to identify the above-mentioned PAN formation processes and attribute local observations to these. Here we present a detailed analysis of PAN observations and meteorological conditions during May 2008 when PAN levels were especially elevated at both sites. The highest PAN concentrations were connected with anticyclonic conditions, which persisted in May 2008 for about 10 days with north-easterly advection towards the sites. A backward dispersion model analysis showed that elevated PAN concentrations were caused by the combination of favourable photochemical production conditions and large precursor concentrations in the European atmospheric boundary layer. The results suggest that the largest PAN values in spring 2008 at both sites were attributable to regional-scale photochemical production of PAN in the (relatively cold) planetary boundary layer from European precursors, whereas the contribution of inter-continental transport or free-tropospheric build-up was of smaller importance for these sites.

Posted on 28 November 2014 | 12:00 am


Competition between water uptake and ice nucleation by glassy organic aerosol particles

Competition between water uptake and ice nucleation by glassy organic aerosol particles

Atmospheric Chemistry and Physics, 14, 12513-12531, 2014

Author(s): T. Berkemeier, M. Shiraiwa, U. Pöschl, and T. Koop

Organic aerosol particles play a key role in climate by serving as nuclei for clouds and precipitation. Their sources and composition are highly variable, and their phase state ranges from liquid to solid under atmospheric conditions, affecting the pathway of activation to cloud droplets and ice crystals. Due to slow diffusion of water in the particle phase, organic particles may deviate in phase and morphology from their thermodynamic equilibrium state, hampering the prediction of their influence on cloud formation. We overcome this problem by combining a novel semi-empirical method for estimation of water diffusivity with a kinetic flux model that explicitly treats water diffusion. We estimate timescales for particle deliquescence as well as various ice nucleation pathways for a wide variety of organic substances, including secondary organic aerosol (SOA) from the oxidation of isoprene, ?-pinene, naphthalene, and dodecane. The simulations show that, in typical atmospheric updrafts, glassy states and solid/liquid core-shell morphologies can persist for long enough that heterogeneous ice nucleation in the deposition and immersion mode can dominate over homogeneous ice nucleation. Such competition depends strongly on ambient temperature and relative humidity as well as humidification rate and particle size. Due to differences in glass transition temperature, hygroscopicity and atomic O / C ratio of the different SOA, naphthalene SOA particles have the highest potential to act as heterogeneous ice nuclei. Our findings demonstrate that kinetic limitations of water diffusion into organic aerosol particles are likely to be encountered under atmospheric conditions and can strongly affect ice nucleation pathways. For the incorporation of ice nucleation by organic aerosol particles into atmospheric models, our results demonstrate a demand for model formalisms that account for the effects of molecular diffusion and not only describe ice nucleation onsets as a function of temperature and relative humidity but also include updraft velocity, particle size and composition.

Posted on 27 November 2014 | 12:00 am


Variations of cloud condensation nuclei (CCN) and aerosol activity during fog–haze episode: a case study from Shanghai

Variations of cloud condensation nuclei (CCN) and aerosol activity during fog–haze episode: a case study from Shanghai

Atmospheric Chemistry and Physics, 14, 12499-12512, 2014

Author(s): C. Leng, Q. Zhang, D. Zhang, C. Xu, T. Cheng, R. Zhang, J. Tao, J. Chen, S. Zha, Y. Zhang, X. Li, L. Kong, and W. Gao

Measurements of cloud condensation nuclei (CCN), condensation nuclei (CN) and aerosol chemical composition were performed simultaneously at an urban site in Shanghai from 6 to 9 November 2010. The variations of CCN number concentration (NCCN) and aerosol activity (activated aerosol fraction, NCCN/NCN) were examined during a fog–haze co-occurring event. Anthropogenic pollutants emitted from vehicles and unfavorable meteorological conditions such as low planetary boundary layer (PBL) height exerted a great influence on PM2.5 and black carbon (BC) loadings. NCCN at 0.2% supersaturation (SS) mostly fell in the range of 994 to 6268 cm?3, and the corresponding NCCN/NCN varied between 0.09 and 0.57. NCCN and NCCN/NCN usually were usually higher in the hazy case due to increased aerosol concentration in the accumulation mode (100–500 nm), and lower in the foggy–hazy and clear cases. The BC mass concentration posed a strong positive effect on NCCN in the foggy–hazy and hazy cases, whereas it poorly correlated with NCCN in the clear case. NCCN/NCN was weakly related with BC in both foggy–hazy and hazy cases. By using a simplified particle hygroscopicity (κ), the calculated critical dry size (CDS) of activated aerosol did not exceed 130 nm at 0.2% SS in spite of diverse aerosol chemical compositions. The predicted NCCN at 0.2% SS was very successful compared with the observed NCCN in clear case (R2=0.96) and foggy–hazy/hazy cases (R2=0.91). In addition, their corresponding ratios of predicted to observed NCCNwere on average 0.95 and 0.92, respectively. More organic matter is possibly responsible for this closure difference between foggy–hazy/hazy and clear cases. These results reveal that the particulate pollutant burden exerts a significant impact on NCCN, especially NCCN/NCN promotes effectively during the polluted periods.

Posted on 27 November 2014 | 12:00 am


Modelled black carbon radiative forcing and atmospheric lifetime in AeroCom Phase II constrained by aircraft observations

Modelled black carbon radiative forcing and atmospheric lifetime in AeroCom Phase II constrained by aircraft observations

Atmospheric Chemistry and Physics, 14, 12465-12477, 2014

Author(s): B. H. Samset, G. Myhre, A. Herber, Y. Kondo, S.-M. Li, N. Moteki, M. Koike, N. Oshima, J. P. Schwarz, Y. Balkanski, S. E. Bauer, N. Bellouin, T. K. Berntsen, H. Bian, M. Chin, T. Diehl, R. C. Easter, S. J. Ghan, T. Iversen, A. Kirkevåg, J.-F. Lamarque, G. Lin, X. Liu, J. E. Penner, M. Schulz, Ø. Seland, R. B. Skeie, P. Stier, T. Takemura, K. Tsigaridis, and K. Zhang

Atmospheric black carbon (BC) absorbs solar radiation, and exacerbates global warming through exerting positive radiative forcing (RF). However, the contribution of BC to ongoing changes in global climate is under debate. Anthropogenic BC emissions, and the resulting distribution of BC concentration, are highly uncertain. In particular, long-range transport and processes affecting BC atmospheric lifetime are poorly understood. Here we discuss whether recent assessments may have overestimated present-day BC radiative forcing in remote regions. We compare vertical profiles of BC concentration from four recent aircraft measurement campaigns to simulations by 13 aerosol models participating in the AeroCom Phase II intercomparison. An atmospheric lifetime of BC of less than 5 days is shown to be essential for reproducing observations in remote ocean regions, in line with other recent studies. Adjusting model results to measurements in remote regions, and at high altitudes, leads to a 25% reduction in AeroCom Phase II median direct BC forcing, from fossil fuel and biofuel burning, over the industrial era. The sensitivity of modelled forcing to BC vertical profile and lifetime highlights an urgent need for further flight campaigns, close to sources and in remote regions, to provide improved quantification of BC effects for use in climate policy.

Posted on 27 November 2014 | 12:00 am


Stratospheric lifetime ratio of CFC-11 and CFC-12 from satellite and model climatologies

Stratospheric lifetime ratio of CFC-11 and CFC-12 from satellite and model climatologies

Atmospheric Chemistry and Physics, 14, 12479-12497, 2014

Author(s): L. Hoffmann, C. M. Hoppe, R. Müller, G. S. Dutton, J. C. Gille, S. Griessbach, A. Jones, C. I. Meyer, R. Spang, C. M. Volk, and K. A. Walker

Chlorofluorocarbons (CFCs) play a key role in stratospheric ozone loss and are strong infrared absorbers that contribute to global warming. The stratospheric lifetimes of CFCs are a measure of their stratospheric loss rates that are needed to determine global warming and ozone depletion potentials. We applied the tracer–tracer correlation approach to zonal mean climatologies from satellite measurements and model data to assess the lifetimes of CFCl3 (CFC-11) and CF2Cl2 (CFC-12). We present estimates of the CFC-11/CFC-12 lifetime ratio and the absolute lifetime of CFC-12, based on a reference lifetime of 52 years for CFC-11. We analyzed climatologies from three satellite missions, the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS), the HIgh Resolution Dynamics Limb Sounder (HIRDLS), and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). We found a CFC-11/CFC-12 lifetime ratio of 0.47±0.08 and a CFC-12 lifetime of 112(96–133) years for ACE-FTS, a ratio of 0.46±0.07 and a lifetime of 113(97–134) years for HIRDLS, and a ratio of 0.46±0.08 and a lifetime of 114(98–136) years for MIPAS. The error-weighted, combined CFC-11/CFC-12 lifetime ratio is 0.46±0.04 and the CFC-12 lifetime estimate is 113(103–124) years. These results agree with the recent Stratosphere-troposphere Processes And their Role in Climate (SPARC) reassessment, which recommends lifetimes of 52(43–67) years and 102(88–122) years, respectively. Having smaller uncertainties than the results from other recent studies, our estimates can help to better constrain CFC-11 and CFC-12 lifetime recommendations in future scientific studies and assessments. Furthermore, the satellite observations were used to validate first simulation results from a new coupled model system, which integrates a Lagrangian chemistry transport model into a climate model. For the coupled model we found a CFC-11/CFC-12 lifetime ratio of 0.48±0.07 and a CFC-12 lifetime of 110(95–129) years, based on a 10-year perpetual run. Closely reproducing the satellite observations, the new model system will likely become a useful tool to assess the impact of advective transport, mixing, and photochemistry as well as climatological variability on the stratospheric lifetimes of long-lived tracers.

Posted on 27 November 2014 | 12:00 am


Low temperatures enhance organic nitrate formation: evidence from observations in the 2012 Uintah Basin Winter Ozone Study

Low temperatures enhance organic nitrate formation: evidence from observations in the 2012 Uintah Basin Winter Ozone Study

Atmospheric Chemistry and Physics, 14, 12441-12454, 2014

Author(s): L. Lee, P. J. Wooldridge, J. B. Gilman, C. Warneke, J. de Gouw, and R. C. Cohen

Nitrogen dioxide (NO2) and total alkyl nitrates (?ANs) were measured using thermal dissociation laser-induced fluorescence during the 2012 Uintah Basin Winter Ozone Study (UBWOS) in Utah, USA. The observed NO2 concentration was highest before sunrise and lowest in the late afternoon, suggestive of a persistent local source of NO2 coupled with turbulent mixing out of the boundary layer. In contrast, ?ANs co-varied with solar radiation with a noontime maximum, indicating that local photochemical production combined with rapid mixing and/or deposition was the dominant factor in determining the ?AN concentrations. We calculate that ?ANs were a large fraction (~60%) of the HOx free radical chain termination and show that the temperature dependence of the alkyl nitrate yields enhances the role of ?ANs in local chemistry during winter by comparison to what would occur in the warmer temperatures of summer.

Posted on 27 November 2014 | 12:00 am


Modeling of gaseous methylamines in the global atmosphere: impacts of oxidation and aerosol uptake

Modeling of gaseous methylamines in the global atmosphere: impacts of oxidation and aerosol uptake

Atmospheric Chemistry and Physics, 14, 12455-12464, 2014

Author(s): F. Yu and G. Luo

Gaseous amines have attracted increasing attention due to their potential role in enhancing particle nucleation and growth and affecting secondary organic aerosol formation. Here we study with a chemistry transport model the global distributions of the most common and abundant amines in the air: monomethylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA). We show that gas phase oxidation and aerosol uptakes are dominant sinks for these methylamines. The oxidation alone (i.e., no aerosol uptake) leads to methylamine lifetimes of 5–10 h in most parts of low and middle latitude regions. The uptake by secondary species with uptake coefficient (?) of 0.03 (corresponding to the uptake by sulfuric acid particles) reduces the lifetime by ~30% over oceans and much more over the major continents, resulting in a methylamine lifetime of less than 1–2 h over central Europe, eastern Asia, and eastern US. With the estimated global emission flux, from the literature, our simulations indicate that [DMA] in the model surface layer over major continents is generally in the range of 0.1–2 ppt (parts per trillion) when ? = 0.03 and 0.2–10 ppt when ? = 0, and decreases quickly with altitude. [DMA] over oceans is below 0.05 ppt and over polar regions it is below 0.01 ppt. The simulated [MMA] is about a factor of ~2.5 higher while [TMA] is a factor of ~8 higher than [DMA]. The modeled concentrations of methylamines are substantially lower than the limited observed values available, with normalized mean bias ranging from ?57 (? = 0) to ?88% (? = 0.03) for MMA and TMA, and from ?78 (? = 0) to ?93% (? = 0.03) for DMA.

Posted on 27 November 2014 | 12:00 am


Air quality simulations of wildfires in the Pacific Northwest evaluated with surface and satellite observations during the summers of 2007 and 2008

Air quality simulations of wildfires in the Pacific Northwest evaluated with surface and satellite observations during the summers of 2007 and 2008

Atmospheric Chemistry and Physics, 14, 12533-12551, 2014

Author(s): F. L. Herron-Thorpe, G. H. Mount, L. K. Emmons, B. K. Lamb, D. A. Jaffe, N. L. Wigder, S. H. Chung, R. Zhang, M. D. Woelfle, and J. K. Vaughan

Evaluation of a regional air quality forecasting system for the Pacific Northwest was carried out using a suite of surface and satellite observations. Wildfire events for the 2007 and 2008 fire seasons were simulated using the Air Information Report for Public Access and Community Tracking v.3 (AIRPACT-3) framework utilizing the Community Multi-scale Air Quality (CMAQ) model. Fire emissions were simulated using the BlueSky framework with fire locations determined by the Satellite Mapping Automated Reanalysis Tool for Fire Incident Reconciliation (SMARTFIRE). Plume rise was simulated using two different methods: the Fire Emission Production Simulator (FEPS) and the Sparse Matrix Operator Kernel Emissions (SMOKE) model. Predicted plume top heights were compared to the Cloud-Aerosol LIDAR with Orthogonal Polarization (CALIOP) instrument aboard the Cloud Aerosol LIDAR and Infrared Pathfinder Satellite Observation (CALIPSO) satellite. Carbon monoxide predictions were compared to the Atmospheric InfraRed Sounder (AIRS) instrument aboard the Aqua satellite. Horizontal distributions of column aerosol optical depth (AOD) were compared to retrievals by the Moderate Resolution Imaging Spectroradiometer (MODIS) instrument aboard the Aqua satellite. Model tropospheric nitrogen dioxide distributions were compared to retrievals from the Ozone Monitoring Instrument (OMI) aboard the Aura satellite. Surface ozone and PM2.5 predictions were compared to surface observations. The AIRPACT-3 model captured the location and transport direction of fire events well, but sometimes missed the timing of fire events and overall underestimated the PM2.5 impact of wildfire events at surface monitor locations. During the 2007 (2008) fire period, the fractional biases (FBs) of AIRPACT-3 for various pollutant observations included: average 24 h PM2.5 FB = ?33% (?27%); maximum daily average 8 h ozone FB = ?8% (+1%); AOD FB = ?61% (?53%); total column CO FB = ?10% (?5%); and tropospheric column NO2 FB = ?39% (?28%). The bias in total column CO is within the range of expected error. Fractional biases of AIRPACT-3 plume tops were found to be ?46% when compared in terms of above mean sea level, but only ?28% when compared in terms of above ground level, partly due to the under-estimation of AIRPACT-3 ground height in complex terrain that results from the 12 km grid-cell smoothing. We conclude that aerosol predictions were too low for locations greater than ~100–300 km downwind from wildfire sources and that model predictions are likely under-predicting secondary organic aerosol (SOA) production, due to a combination of very low volatile organic compound (VOC) emission factors used in the United States Forest Service Consume model, an incomplete speciation of VOC to SOA precursors in SMOKE, and under-prediction by the SOA parameterization within CMAQ.

Posted on 27 November 2014 | 12:00 am


A new parameterization of particle dry deposition over rough surfaces

A new parameterization of particle dry deposition over rough surfaces

Atmospheric Chemistry and Physics, 14, 12429-12440, 2014

Author(s): J. Zhang and Y. Shao

In existing particle dry deposition schemes, the effects of gravity and surface roughness elements on particle motion are often poorly represented. In this study, we propose a new scheme to overcome such deficiencies. Particle deposition velocity is a function of aerodynamic, surface-collection and gravitational resistances. In this study, the effect of gravitation settling is treated analytically. More importantly, the new scheme takes into consideration the impacts of roughness elements on turbulent particle diffusion and surface particle collection. A relationship between aerodynamic and surface-collection processes is established by using an analogy between drag partition and deposition-flux partition. The scheme is then tested against a wind-tunnel data set for four different surfaces and a good agreement between the scheme predictions and the observations is found. The sensitivity of the scheme to the input parameters is tested. Important factors which affect particle deposition in different particle size ranges are identified. The scheme shows good capacity for modeling particle deposition over rough surfaces.

Posted on 27 November 2014 | 12:00 am


Chemistry and mineralogy of clay minerals in Asian and Saharan dusts and the implications for iron supply to the oceans

Chemistry and mineralogy of clay minerals in Asian and Saharan dusts and the implications for iron supply to the oceans

Atmospheric Chemistry and Physics, 14, 12415-12428, 2014

Author(s): G. Y. Jeong and E. P. Achterberg

Mineral dust supplied to remote ocean regions stimulates phytoplankton growth through delivery of micronutrients, notably iron (Fe). Although attention is usually paid to Fe (hydr)oxides as major sources of available Fe, Fe-bearing clay minerals are typically the dominant phase in mineral dust. The mineralogy and chemistry of clay minerals in dust particles, however, are largely unknown. We conducted microscopic identification and chemical analysis of the clay minerals in Asian and Saharan dust particles. Cross-sectional slices of dust particles were prepared by focused ion beam (FIB) techniques and analyzed by transmission electron microscopy (TEM) combined with energy dispersive X-ray spectroscopy (EDXS). TEM images of FIB slices revealed that clay minerals occurred as either nano-thin platelets or relatively thick plates. Chemical compositions and lattice fringes of the nano-thin platelets suggested that they included illite, smectite, illite–smectite mixed layers, and their nanoscale mixtures (illite–smectite series clay minerals, ISCMs) which could not be resolved with an electron microbeam. EDXS chemical analysis of the clay mineral grains revealed that the average Fe content was 5.8% in nano-thin ISCM platelets assuming 14% H2O, while the Fe content of illite and chlorite was 2.8 and 14.8%, respectively. In addition, TEM and EDXS analyses were performed on clay mineral grains dispersed and loaded on micro-grids. The average Fe content of clay mineral grains was 6.7 and 5.4% in Asian and Saharan dusts, respectively. A comparative X-ray diffraction analysis of bulk dusts showed that Saharan dust was more enriched in clay minerals than Asian dust, while Asian dust was more enriched in chlorite. Clay minerals, in particular nanocrystalline ISCMs and Fe-rich chlorite, are probably important sources of Fe to remote marine ecosystems. Further detailed analyses of the mineralogy and chemistry of clay minerals in global mineral dusts are required to evaluate the inputs of Fe to surface ocean microbial communities.

Posted on 27 November 2014 | 12:00 am


Regional climate model assessment of the urban land-surface forcing over central Europe

Regional climate model assessment of the urban land-surface forcing over central Europe

Atmospheric Chemistry and Physics, 14, 12393-12413, 2014

Author(s): P. Huszar, T. Halenka, M. Belda, M. Zak, K. Sindelarova, and J. Miksovsky

For the purpose of qualifying and quantifying the climate impact of cities and urban surfaces in general on climate of central Europe, the surface parameterization in regional climate model RegCM4 has been extended with the Single-layer Urban Canopy Model (SLUCM). A set of experiments was performed over the period of 2005–2009 for central Europe, either without considering urban surfaces or with the SLUCM treatment. Results show a statistically significant impact of urbanized surfaces on temperature (up to 1.5 K increase in summer) as well as on the boundary layer height (increases up to 50 m). Urbanization further influences surface wind with a winter decrease up to ?0.6 m s?1, though both increases and decreases were detected in summer depending on the location relative to the cities and daytime (changes up to 0.3 m s?1). Urban surfaces significantly reduce the humidity over the surface. This impacts the simulated summer precipitation rate, showing a decrease over cities of up to ?2 mm day?1. Significant temperature increases are simulated over higher altitudes as well, not only within the urban canopy layer. With the urban parameterization, the climate model better describes the diurnal temperature variation, reducing the cold afternoon and evening bias of RegCM4.

Sensitivity experiments were carried out to quantify the response of the meteorological conditions to changes in the parameters specific to the urban environment, such as street width, building height, albedo of the roofs and anthropogenic heat release. The results proved to be rather robust and the choice of the key SLUCM parameters impacts them only slightly (mainly temperature, boundary layer height and wind velocity). Statistically significant impacts are modelled not only over large urbanized areas, but the influence of the cities is also evident over rural areas without major urban surfaces. It is shown that this is the result of the combined effect of the distant influence of the cities and the influence of the minor local urban surface coverage.

Posted on 26 November 2014 | 12:00 am


Measurements of OH and RO2 radicals at Dome C, East Antarctica

Measurements of OH and RO2 radicals at Dome C, East Antarctica

Atmospheric Chemistry and Physics, 14, 12373-12392, 2014

Author(s): A. Kukui, M. Legrand, S. Preunkert, M. M. Frey, R. Loisil, J. Gil Roca, B. Jourdain, M. D. King, J. L. France, and G. Ancellet

Concentrations of OH radicals and the sum of peroxy radicals, RO2, were measured in the boundary layer for the first time on the East Antarctic Plateau at the Concordia Station (Dome C, 75.10° S, 123.31° E) during the austral summer 2011/2012. The median concentrations of OH and RO2 radicals were 3.1 × 106 molecule cm?3 and 9.9 × 106 molecule cm?3, respectively. These values are comparable to those observed at the South Pole, confirming that the elevated oxidative capacity of the Antarctic atmospheric boundary layer found at the South Pole is not restricted to the South Pole but common over the high Antarctic plateau. At Concordia, the concentration of radicals showed distinct diurnal profiles with the median maximum of 5.2 × 106 molecule cm?3 at 11:00 and the median minimum of 1.1 × 106 molecule cm?3 at 01:00 for OH radicals and 1.7 × 108 molecule cm?3 and 2.5 × 107 molecule cm?3 for RO2 radicals at 13:00 and 23:00, respectively (all times are local times). Concurrent measurements of O3, HONO, NO, NO2, HCHO and H2O2 demonstrated that the major primary source of OH and RO2 radicals at Dome C was the photolysis of HONO, HCHO and H2O2, with the photolysis of HONO contributing ~75% of total primary radical production. However, photochemical modelling with accounting for all these radical sources overestimates the concentrations of OH and RO2 radicals by a factor of 2 compared to field observations. Neglecting the net OH production from HONO in the photochemical modelling results in an underestimation of the concentrations of OH and RO2 radicals by a factor of 2. To explain the observations of radicals in this case an additional source of OH equivalent to about (25–35)% of measured photolysis of HONO is required. Even with a factor of 5 reduction in the concentrations of HONO, the photolysis of HONO represents the major primary radical source at Dome C. To account for a possibility of an overestimation of NO2 observed at Dome C the calculations were also performed with NO2 concentrations estimated by assuming steady-state NO2 / NO ratios. In this case the net radical production from the photolysis of HONO should be reduced by a factor of 5 or completely removed based on the photochemical budget of OH or 0-D modelling, respectively. Another major factor leading to the large concentration of OH radicals measured at Dome C was large concentrations of NO molecules and fast recycling of peroxy radicals to OH radicals.

Posted on 26 November 2014 | 12:00 am


Mesoscopic surface roughness of ice crystals pervasive across a wide range of ice crystal conditions

Mesoscopic surface roughness of ice crystals pervasive across a wide range of ice crystal conditions

Atmospheric Chemistry and Physics, 14, 12357-12371, 2014

Author(s): N. B. Magee, A. Miller, M. Amaral, and A. Cumiskey

Here we show high-magnification images of hexagonal ice crystals acquired by environmental scanning electron microscopy (ESEM). Most ice crystals were grown and sublimated in the water vapor environment of an FEI-Quanta-200 ESEM, but crystals grown in a laboratory diffusion chamber were also transferred intact and imaged via ESEM. All of these images display prominent mesoscopic topography including linear striations, ridges, islands, steps, peaks, pits, and crevasses; the roughness is not observed to be confined to prism facets. The observations represent the most highly magnified images of ice surfaces yet reported and expand the range of conditions in which rough surface features are known to be conspicuous. Microscale surface topography is seen to be ubiquitously present at temperatures ranging from ?10 °C to ?40 °C, in supersaturated and subsaturated conditions, on all crystal facets, and irrespective of substrate. Despite the constant presence of surface roughness, the patterns of roughness are observed to be dramatically different between growing and sublimating crystals, and transferred crystals also display qualitatively different patterns of roughness. Crystals are also demonstrated to sometimes exhibit inhibited growth in moderately supersaturated conditions following exposure to near-equilibrium conditions, a phenomenon interpreted as evidence of 2-D nucleation. New knowledge about the characteristics of these features could affect the fundamental understanding of ice surfaces and their physical parameterization in the context of satellite retrievals and cloud modeling. Links to supplemental videos of ice growth and sublimation are provided.

Posted on 25 November 2014 | 12:00 am


Particle surface area dependence of mineral dust in immersion freezing mode: investigations with freely suspended drops in an acoustic levitator and a vertical wind tunnel

Particle surface area dependence of mineral dust in immersion freezing mode: investigations with freely suspended drops in an acoustic levitator and a vertical wind tunnel

Atmospheric Chemistry and Physics, 14, 12343-12355, 2014

Author(s): K. Diehl, M. Debertshäuser, O. Eppers, H. Schmithüsen, S. K. Mitra, and S. Borrmann

The heterogeneous freezing temperatures of supercooled drops were measured using an acoustic levitator. This technique allows one to freely suspend single drops in the air without any wall contact. Heterogeneous nucleation by two types of illite (illite IMt1 and illite NX) and a montmorillonite sample was investigated in the immersion mode. Drops of 1 mm in radius were monitored by a video camera while cooled down to ?28 °C to simulate freezing within the tropospheric temperature range. The surface temperature of the drops was contact-free, determined with an infrared thermometer; the onset of freezing was indicated by a sudden increase of the drop surface temperature. For comparison, measurements with one particle type (illite NX) were additionally performed in the Mainz vertical wind tunnel with drops of 340 ?m radius freely suspended. Immersion freezing was observed in a temperature range between ?13 and ?26 °C as a function of particle type and particle surface area immersed in the drops. Isothermal experiments in the wind tunnel indicated that after the cooling stage freezing still proceeds, at least during the investigated time period of 30 s. The results were evaluated by applying two descriptions of heterogeneous freezing, the stochastic and the singular model. Although the wind tunnel results do not support the time-independence of the freezing process both models are applicable for comparing the results from the two experimental techniques.

Posted on 25 November 2014 | 12:00 am


Enhancements of the refractory submicron aerosol fraction in the Arctic polar vortex: feature or exception?

Enhancements of the refractory submicron aerosol fraction in the Arctic polar vortex: feature or exception?

Atmospheric Chemistry and Physics, 14, 12319-12342, 2014

Author(s): R. Weigel, C. M. Volk, K. Kandler, E. Hösen, G. Günther, B. Vogel, J.-U. Grooß, S. Khaykin, G. V. Belyaev, and S. Borrmann

In situ measurements with a four-channel stratospheric condensation particle counter (CPC) were conducted at up to 20 km altitude on board the aircraft M-55 Geophysica from Kiruna, Sweden, in January through March (EUPLEX 2003, RECONCILE 2010) and in December (ESSenCe 2011). During all campaigns air masses from the upper stratosphere and mesosphere were subsiding inside the Arctic winter vortex, thus initializing a transport of refractory aerosol into the lower stratosphere (? < 500 K). The strength and extent of this downward transport varied between the years depending on the dynamical evolution of the vortex. Inside the vortex and at potential temperatures ? ? 450 K around 11 submicron particles per cm3 were generally detected. Up to 8 of these 11 particles per cm3 were found to contain thermo-stable (at 250 °C) residuals with diameters of 10 nm to about 1 ?m. Particle mixing ratios (150 mg?1) and fractions of non-volatile particles (75% of totally detected particles) exhibited highest values in air masses having the lowest content of nitrous oxide (70 nmol mol?1 of N2O). This indicates that refractory aerosol originates from the upper stratosphere or the mesosphere. Derived from the mixing ratio of the simultaneously measured long-lived tracer N2O, an empirical index serves to differentiate probed air masses according to their origin: inside the vortex, the vortex edge region, or outside the vortex. Previously observed high fractions of refractory submicron aerosol in the 2003 Arctic vortex were ascribed to unusually strong subsidence during that winter. However, measurements under perturbed vortex conditions in 2010 and during early winter in December 2011 revealed similarly high values. Thus, the abundance of refractory aerosol in the lower stratosphere within the Arctic vortices appears to be a regular feature rather than the exception. During December, the import from aloft into the lower stratosphere appears to be developing; thereafter the abundance of refractory aerosol inside the vortex reaches its highest levels in March. The correlations of refractory aerosol with N2O suggest that, apart from mean subsidence, diabatic dispersion inside the vortex significantly contributes to the transport of particles to the Arctic lower stratosphere. A measurement-based estimate of the total mass of refractory aerosol inside the vortex is provided for each campaign. Based on the derived increase of particle mass in the lower stratospheric vortex (100–67 hPa pressure altitude) by a factor of 4.5 between early and late winter, we estimate the total mass of mesospheric particles deposited over the winter 2009/2010 in the entire Arctic vortex to range between 77 × 103 and 375 × 106 kg. This estimate is compared with the expected atmospheric influx of meteoritic material (110 ± 55 × 103 kg per day). Such estimates at present still hold considerable uncertainties, which are discussed in this article. Nevertheless, the results enable placing constraints on the shape of the so far unknown size distribution of refractory aerosol within the vortex.

Posted on 25 November 2014 | 12:00 am


CCN activity of size-selected aerosol at a Pacific coastal location

CCN activity of size-selected aerosol at a Pacific coastal location

Atmospheric Chemistry and Physics, 14, 12307-12317, 2014

Author(s): J. D. Yakobi-Hancock, L. A. Ladino, A. K. Bertram, J. A. Huffman, K. Jones, W. R. Leaitch, R. H. Mason, C. L. Schiller, D. Toom-Sauntry, J. P. S. Wong, and J. P. D. Abbatt

As one aspect of the NETwork on Climate and Aerosols: addressing key uncertainties in Remote Canadian Environments (NETCARE), measurements of the cloud condensation nucleation properties of 50 and 100 nm aerosol particles were conducted at Ucluelet on the west coast of Vancouver Island in August 2013. The overall hygroscopicity parameter of the aerosol (κambient) exhibited a wide variation, ranging from 0.14 ± 0.05 to 1.08 ± 0.40 (where the uncertainty represents the systematic error). The highest ? values arose when the organic-to-sulfate ratio of the aerosol was lowest and when winds arrived from the west after transport through the marine boundary layer. The average κambient during this time was 0.57 ± 0.16, where the uncertainty represents the standard deviation. At most other times, the air was predominantly influenced by both marine and continental emissions, which had lower average PM1 κambient values (max value, 0.41 ± 0.08). The two-day average aerosol ionic composition also showed variation, but was consistently acidic and dominated by ammonium (18–56% by mole) and sulfate (19–41% by mole), with only minor levels of sodium or chloride. Average κorg (hygroscopicity parameter for the aerosol's organic component) values were estimated using PM1 aerosol composition data and by assuming that the ratio of aerosol organic to sulfate mass is related directly to the composition of the size-selected particles.

Posted on 24 November 2014 | 12:00 am


Modeling of HCHO and CHOCHO at a semi-rural site in southern China during the PRIDE-PRD2006 campaign

Modeling of HCHO and CHOCHO at a semi-rural site in southern China during the PRIDE-PRD2006 campaign

Atmospheric Chemistry and Physics, 14, 12291-12305, 2014

Author(s): X. Li, F. Rohrer, T. Brauers, A. Hofzumahaus, K. Lu, M. Shao, Y. H. Zhang, and A. Wahner

HCHO and CHOCHO are important trace gases in the atmosphere, serving as tracers of VOC oxidations. In the past decade, high concentrations of HCHO and CHOCHO have been observed for the Pearl River Delta (PRD) region in southern China. In this study, we performed box model simulations of HCHO and CHOCHO at a semi-rural site in the PRD, focusing on understanding their sources and sinks and factors influencing the CHOCHO to HCHO ratio (RGF). The model was constrained by the simultaneous measurements of trace gases and radicals. Isoprene oxidation by OH radicals is the major pathway forming HCHO, followed by degradations of alkenes, aromatics, and alkanes. The production of CHOCHO is dominated by isoprene and aromatic degradation; contributions from other NMHCs are of minor importance. Compared to the measurement results, the model predicts significant higher HCHO and CHOCHO concentrations. Sensitivity studies suggest that fresh emissions of precursor VOCs, uptake of HCHO and CHOCHO by aerosols, fast vertical transport, and uncertainties in the treatment of dry deposition all have the potential to contribute significantly to this discrepancy. Our study indicates that, in addition to chemical considerations (i.e., VOC composition, OH and NOx levels), atmospheric physical processes (e.g., transport, dilution, deposition) make it difficult to use the CHOCHO to HCHO ratio as an indicator for the origin of air mass composition.

Posted on 21 November 2014 | 12:00 am


Recent trends in aerosol optical properties derived from AERONET measurements

Recent trends in aerosol optical properties derived from AERONET measurements

Atmospheric Chemistry and Physics, 14, 12271-12289, 2014

Author(s): J. Li, B. E. Carlson, O. Dubovik, and A. A. Lacis

The Aerosol Robotic Network (AERONET) has been providing high-quality retrievals of aerosol optical properties from the surface at worldwide locations for more than a decade. Many sites have continuous and consistent records for more than 10 years, which enables the investigation of long-term trends in aerosol properties at these locations. In this study, we present the results of a trend analysis at selected stations with long data records. In addition to commonly studied parameters such as aerosol optical depth (AOD) and Ångström exponent (AE), we also focus on inversion products including absorption aerosol optical depth (ABS), single-scattering albedo (SSA) and the absorption Ångström exponent (AAE). Level 2.0 quality assured data are the primary source. However, due to the scarcity of level 2.0 inversion products resulting from the strict AOD quality control threshold, we have also analyzed level 1.5 data, with some quality control screening to provide a reference for global results. Two statistical methods are used to detect and estimate the trend: the Mann–Kendall test associated with Sen's slope and linear least-squares fitting. The results of these statistical tests agree well in terms of the significance of the trend for the majority of the cases. The results indicate that Europe and North America experienced a uniform decrease in AOD, while significant (>90%) increases in these two parameters are found for North India and the Arabian Peninsula. The AE trends turn out to be different for North America and Europe, with increases for the former and decreases for the latter, suggesting opposite changes in fine/coarse-mode fraction. For level 2.0 inversion parameters, Beijing and Kanpur both experienced an increase in SSA. Beijing also shows a reduction in ABS, while the SSA increase for Kanpur is mainly due the increase in scattering aerosols. Increased absorption and reduced SSA are found at Solar_Village. At level 1.5, most European and North American sites also show positive SSA and negative ABS trends, although the data are more uncertain. The AAE trends are less spatially coherent due to large uncertainties, except for a robust increase at three sites in West Africa, which suggests a possible reduction in black carbon. Overall, the trends do not exhibit obvious seasonality for the majority of parameters and stations.

Posted on 21 November 2014 | 12:00 am


Relations between erythemal UV dose, global solar radiation, total ozone column and aerosol optical depth at Uccle, Belgium

Relations between erythemal UV dose, global solar radiation, total ozone column and aerosol optical depth at Uccle, Belgium

Atmospheric Chemistry and Physics, 14, 12251-12270, 2014

Author(s): V. De Bock, H. De Backer, R. Van Malderen, A. Mangold, and A. Delcloo

At Uccle, Belgium, a long time series (1991–2013) of simultaneous measurements of erythemal ultraviolet (UV) dose (Sery), global solar radiation (Sg), total ozone column (Q_{O3}$) and aerosol optical depth (τaer) (at 320.1 nm) is available, which allows for an extensive study of the changes in the variables over time. Linear trends were determined for the different monthly anomalies time series. Sery, Sg and QO3 all increase by respectively 7, 4 and 3% per decade. τaer shows an insignificant negative trend of ?8% per decade. These trends agree with results found in the literature for sites with comparable latitudes. A change-point analysis, which determines whether there is a significant change in the mean of the time series, is applied to the monthly anomalies time series of the variables. Only for Sery and QO3, was a significant change point present in the time series around February 1998 and March 1998, respectively. The change point in QO3 corresponds with results found in the literature, where the change in ozone levels around 1997 is attributed to the recovery of ozone. A multiple linear regression (MLR) analysis is applied to the data in order to study the influence of Sg, QO3 and τaer on Sery. Together these parameters are able to explain 94% of the variation in Sery. Most of the variation (56%) in Sery is explained by Sg. The regression model performs well, with a slight tendency to underestimate the measured Sery values and with a mean absolute bias error (MABE) of 18%. However, in winter, negative Sery are modeled. Applying the MLR to the individual seasons solves this issue. The seasonal models have an adjusted R2 value higher than 0.8 and the correlation between modeled and measured Sery values is higher than 0.9 for each season. The summer model gives the best performance, with an absolute mean error of only 6%. However, the seasonal regression models do not always represent reality, where an increase in Sery is accompanied with an increase in QO3 and a decrease in τaer. In all seasonal models, Sg is the factor that contributes the most to the variation in Sery, so there is no doubt about the necessity to include this factor in the regression models. The individual contribution of τaer to Sery is very low, and for this reason it seems unnecessary to include τaer in the MLR analysis. Including QO3, however, is justified to increase the adjusted R2 and to decrease the MABE of the model.

Posted on 20 November 2014 | 12:00 am


Chemical composition and mass size distribution of PM1 at an elevated site in central east China

Chemical composition and mass size distribution of PM1 at an elevated site in central east China

Atmospheric Chemistry and Physics, 14, 12237-12249, 2014

Author(s): Y. M. Zhang, X. Y. Zhang, J. Y. Sun, G. Y. Hu, X. J. Shen, Y. Q. Wang, T. T. Wang, D. Z. Wang, and Y. Zhao

Size-resolved aerosol chemical compositions were measured continuously for 1.5 years from June 2010 to January 2012 with an aerosol mass spectrometer (AMS) to characterize the mass and size distributions (MSDs) of major chemical components in submicron particles (approximately PM1) at Mountain Tai (Mt. Tai), an elevated site in central east China. The annual mean mass concentrations of organic, sulfate, nitrate, ammonium, and chloride were 11.2, 9.2, 7.2, 5.8, and 0.95 ?g m?3, respectively, which are much higher than those at most mountain sites in the USA and Europe, but lower than those at the nearby surface rural sites in China. A clear seasonality was observed for all major components throughout the study, with low concentration in fall and high in summer, and is believed to be caused by seasonal variations in planetary boundary layer (PBL) height, near surface pollutant concentrations and regional transport processes. Air masses were classified into categories impacted by PBL, lower free troposphere (LFT), new particle formation (NPF), in-cloud processes, and polluted aerosols. Organics dominated the PM1 mass during the NPF episodes, while sulfate contributed most to PM1 in cloud events. The average MSDs of particles between 30 and 1000 nm during the entire study for organics, sulfate, nitrate, and ammonium were approximately log-normal with mass median diameters (MMDs) of 539, 585, 542, and 545 nm, respectively. These values are slightly larger than those observed at ground sites within the North China Plain (NCP), likely due to the relative aged and well-mixed aerosol masses at Mt. Tai. There were no obvious differences in MMDs during the PBL, LFT, in-cloud and polluted episodes, but smaller MMDs, especially for organics, were observed during the NPF events. During the PBL, NPF, and polluted episodes, organics accounted for major proportions at smaller modes, and reached 70% at 100–200 nm particles in the polluted events. In cloud episodes, inorganics contributed 70% to the whole size range dominated by sulfate, which contributed 40% to small particles (100–200 nm), while organics occupied 20%, indicating that sulfate is a critical chemical component in cloud formation. Seven clusters of air masses were classified based on 72 h back-trajectory analysis. The majority of the regionally dispersed aerosols were found to be contributed from short distance mixed aerosols, mostly originated from the south with organics and sulfate as major components. Air masses from long range transport always brought clean and dry aerosols which resulted in low concentrations at Mt. Tai. AMS-PMF (positive matrix factorization) was employed to resolve the subtype of organics. Oxygenic organics aerosols (OAs) occupied 49, 56, 51, and 41% of OAs in the four seasons respectively, demonstrating that most OA were oxidized in summer due to strong photochemical reactions. Biomass burning OAs (BBOAs) accounted for 34% of OA in summer, mainly from field burning of agriculture residues, and coal combustion OAs (CCOAs) accounted for 22% of OA in winter from heating.

Posted on 20 November 2014 | 12:00 am


Cirrus and water vapour transport in the tropical tropopause layer – Part 2: Roles of ice nucleation and sedimentation, cloud dynamics, and moisture conditions

Cirrus and water vapour transport in the tropical tropopause layer – Part 2: Roles of ice nucleation and sedimentation, cloud dynamics, and moisture conditions

Atmospheric Chemistry and Physics, 14, 12225-12236, 2014

Author(s): T. Dinh, S. Fueglistaler, D. Durran, and T. Ackerman

A high-resolution, two-dimensional numerical model is used to study the moisture redistribution following homogeneous ice nucleation induced by Kelvin waves in the tropical tropopause layer (TTL). We compare results for dry/moist initial conditions and three levels of complexity for the representation of cloud processes: complete microphysics and cloud radiative effects, likewise but without radiative effects, and instantaneous removal of moisture in excess of saturation upon nucleation.

Cloud evolution and moisture redistribution are found to be sensitive to initial conditions and cloud processes. Ice sedimentation leads to a downward flux of water, whereas the cloud radiative heating induces upward advection of the cloudy air. The latter results in an upward (downward) flux of water vapour if the cloudy air is moister (drier) than the environment, which is typically when the environment is subsaturated (supersaturated).

Only a fraction (~25% or less) of the cloud experiences nucleation. Post-nucleation processes (ice depositional growth, sedimentation, and sublimation) are important to cloud morphology, and both dehydrated and hydrated layers may be indicators of TTL cirrus occurrence. The calculation with instantaneous removal of moisture not only misses the hydration but also underestimates dehydration due to (i) nucleation before reaching the minimum saturation mixing ratio, and (ii) lack of moisture removal from sedimenting ice particles below the nucleation level.

The sensitivity to initial conditions and cloud processes suggests that it is difficult to reach generic, quantitative estimates of cloud-induced moisture redistribution on the basis of case-by-case calculations.

Posted on 20 November 2014 | 12:00 am


Missing SO2 oxidant in the coastal atmosphere? – observations from high-resolution measurements of OH and atmospheric sulfur compounds

Missing SO2 oxidant in the coastal atmosphere? – observations from high-resolution measurements of OH and atmospheric sulfur compounds

Atmospheric Chemistry and Physics, 14, 12209-12223, 2014

Author(s): H. Berresheim, M. Adam, C. Monahan, C. O'Dowd, J. M. C. Plane, B. Bohn, and F. Rohrer

Diurnal and seasonal variations of gaseous sulfuric acid (H2SO4) and methane sulfonic acid (MSA) were measured in NE Atlantic air at the Mace Head atmospheric research station during the years 2010 and 2011. The measurements utilized selected-ion chemical ionization mass spectrometry (SI/CIMS) with a detection limit for both compounds of 4.3 × 104 cm?3 at 5 min signal integration. The H2SO4 and MSA gas-phase concentrations were analyzed in conjunction with the condensational sink for both compounds derived from 3 nm to 10 ?m (aerodynamic diameter) aerosol size distributions. Accommodation coefficients of 1.0 for H2SO4 and 0.12 for MSA were assumed, leading to estimated atmospheric lifetimes on the order of 7 and 25 min, respectively. With the SI/CIMS instrument in OH measurement mode alternating between OH signal and background (non-OH) signal, evidence was obtained for the presence of one or more unknown oxidants of SO2 in addition to OH. Depending on the nature of the oxidant(s), its ambient concentration may be enhanced in the CIMS inlet system by additional production. The apparent unknown SO2 oxidant was additionally confirmed by direct measurements of SO2 in conjunction with calculated H2SO4 concentrations. The calculated H2SO4 concentrations were consistently lower than the measured concentrations by a factor of 4.7 ± 2.4 when considering the oxidation of SO2 by OH as the only source of H2SO4. Both the OH and the background signal were also observed to increase significantly during daytime aerosol nucleation events, independent of the ozone photolysis frequency, J(O1D), and were followed by peaks in both H2SO4 and MSA concentrations. This suggests a strong relation between the unknown oxidant(s), OH chemistry, and the atmospheric photolysis and photooxidation of biogenic iodine compounds. As to the identity of the atmospheric SO2 oxidant(s), we have been able to exclude ClO, BrO, IO, and OIO as possible candidates based on {ab initio} calculations. Never\-theless, IO could contribute significantly to the observed CIMS background signal. A detailed analysis of this CIMS background signal in context with recently published kinetic data currently suggests that Criegee intermediates (CIs) produced from ozonolysis of alkenes play no significant role for SO2 oxidation in the marine atmosphere at Mace Head. On the other hand, SO2 oxidation by small CIs such as CH2OO produced photolytically or possibly in the photochemical degradation of methane is consistent with our observations. In addition, H2SO4 formation from dimethyl sulfide oxidation via SO3 as an intermediate instead of SO2 also appears to be a viable explanation. Both pathways need to be further explored.

Posted on 20 November 2014 | 12:00 am





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