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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:



Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

Atmospheric Chemistry and Physics, 15, 4225-4239, 2015

Author(s): A. L. Van Wyngarden, S. Pérez-Montaño, J. V. H. Bui, E. S. W. Li, T. E. Nelson, K. T. Ha, L. Leong, and L. T. Iraci

Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40–80 wt%) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance–Fourier transform infrared (ATR-FTIR) and 1H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and methylglyoxal have the potential to produce significant organic aerosol mass and therefore could potentially impact chemical, optical and/or cloud-forming properties of aerosols, especially if the products partition to the aerosol surface.

Posted on 24 April 2015 | 12:00 am


An overview of regional and local characteristics of aerosols in South Africa using satellite, ground, and modeling data

An overview of regional and local characteristics of aerosols in South Africa using satellite, ground, and modeling data

Atmospheric Chemistry and Physics, 15, 4259-4278, 2015

Author(s): S. P. Hersey, R. M. Garland, E. Crosbie, T. Shingler, A. Sorooshian, S. Piketh, and R. Burger

We present a comprehensive overview of particulate air quality across the five major metropolitan areas of South Africa (Cape Town, Bloemfontein, Johannesburg and Tshwane (Gauteng Province), the Industrial Highveld Air Quality Priority Area (HVAPA), and Durban), based on a decadal (1 January 2000 to 31 December 2009) aerosol climatology from multiple satellite platforms and detailed analysis of ground-based data from 19 sites throughout Gauteng Province. Satellite analysis was based on aerosol optical depth (AOD) from MODIS Aqua and Terra (550 nm) and MISR (555 nm) platforms, Ångström Exponent (?) from MODIS Aqua (550/865 nm) and Terra (470/660 nm), ultraviolet aerosol index (UVAI) from TOMS, and results from the Goddard Ozone Chemistry Aerosol Radiation and Transport (GOCART) model. At continentally influenced sites, AOD, ?, and UVAI reach maxima (0.12–0.20, 1.0–1.8, and 1.0–1.2, respectively) during austral spring (September–October), coinciding with a period of enhanced dust generation and the maximum integrated intensity of close-proximity and subtropical fires identified by MODIS Fire Information for Resource Management System (FIRMS). Minima in AOD, ?, and UVAI occur during winter. Results from ground monitoring indicate that low-income township sites experience by far the worst particulate air quality in South Africa, with seasonally averaged PM10 concentrations as much as 136% higher in townships that in industrial areas.

We report poor agreement between satellite and ground aerosol measurements, with maximum surface aerosol concentrations coinciding with minima in AOD, ?, and UVAI. This result suggests that remotely sensed data are not an appropriate surrogate for ground air quality in metropolitan South Africa.

Posted on 24 April 2015 | 12:00 am


Modeling the feedback between aerosol and meteorological variables in the atmospheric boundary layer during a severe fog–haze event over the North China Plain

Modeling the feedback between aerosol and meteorological variables in the atmospheric boundary layer during a severe fog–haze event over the North China Plain

Atmospheric Chemistry and Physics, 15, 4279-4295, 2015

Author(s): Y. Gao, M. Zhang, Z. Liu, L. Wang, P. Wang, X. Xia, M. Tao, and L. Zhu

The feedback between aerosol and meteorological variables in the atmospheric boundary layer over the North China Plain (NCP) is analyzed by conducting numerical experiments with and without the aerosol direct and indirect effects via a coupled meteorology and aerosol/chemistry model (WRF-Chem). The numerical experiments are performed for the period of 2–26 January 2013, during which a severe fog–haze event (10–15 January 2013) occurred, with the simulated maximum hourly surface PM2.5 concentration of ~600 ug m?3, minimum atmospheric visibility of ~0.3 km, and 10–100 hours of simulated hourly surface PM2.5 concentration above 300 ug m?3 over NCP. A comparison of model results with aerosol feedback against observations indicates that the model can reproduce the spatial and temporal characteristics of temperature, relative humidity (RH), wind, surface PM2.5 concentration, atmospheric visibility, and aerosol optical depth reasonably well. Analysis of model results with and without aerosol feedback shows that during the fog–haze event aerosols lead to a significant negative radiative forcing of ?20 to ?140 W m?2 at the surface and a large positive radiative forcing of 20–120 W m?2 in the atmosphere and induce significant changes in meteorological variables with maximum changes during 09:00–18:00 local time (LT) over urban Beijing and Tianjin and south Hebei: the temperature decreases by 0.8–2.8 °C at the surface and increases by 0.1–0.5 °C at around 925 hPa, while RH increases by about 4–12% at the surface and decreases by 1–6% at around 925 hPa. As a result, the aerosol-induced equivalent potential temperature profile change shows that the atmosphere is much more stable and thus the surface wind speed decreases by up to 0.3 m s?1 (10%) and the atmosphere boundary layer height decreases by 40–200 m (5–30%) during the daytime of this severe fog–haze event. Owing to this more stable atmosphere during 09:00–18:00, 10–15~January, compared to the surface PM2.5 concentration from the model results without aerosol feedback, the average surface PM2.5 concentration increases by 10–50 ?g m?3 (2–30%) over Beijing, Tianjin, and south Hebei and the maximum increase of hourly surface PM2.5 concentration is around 50 (70%), 90 (60%), and 80 ?g m?3 (40%) over Beijing, Tianjin, and south Hebei, respectively. Although the aerosol concentration is maximum at nighttime, the mechanism of feedback, by which meteorological variables increase the aerosol concentration most, occurs during the daytime (around 10:00 and 16:00 LT). The results suggest that aerosol induces a more stable atmosphere, which is favorable for the accumulation of air pollutants, and thus contributes to the formation of fog–haze events.

Posted on 24 April 2015 | 12:00 am


Study of a prototypical convective boundary layer observed during BLLAST: contributions by large-scale forcings

Study of a prototypical convective boundary layer observed during BLLAST: contributions by large-scale forcings

Atmospheric Chemistry and Physics, 15, 4241-4257, 2015

Author(s): H. P. Pietersen, J. Vilà-Guerau de Arellano, P. Augustin, A. van de Boer, O. de Coster, H. Delbarre, P. Durand, M. Fourmentin, B. Gioli, O. Hartogensis, F. Lohou, M. Lothon, H. G. Ouwersloot, D. Pino, and J. Reuder

We study the influence of the large-scale atmospheric contribution to the dynamics of the convective boundary layer (CBL) in a situation observed during the Boundary Layer Late Afternoon and Sunset Turbulence (BLLAST) field campaign. We employ two modeling approaches, the mixed-layer theory and large-eddy simulation (LES), with a complete data set of surface and upper-air atmospheric observations, to quantify the contributions of the advection of heat and moisture, and subsidence. We find that by only taking surface and entrainment fluxes into account, the boundary-layer height is overestimated by 70%. Constrained by surface and upper-air observations, we infer the large-scale vertical motions and horizontal advection of heat and moisture. Our findings show that subsidence has a clear diurnal pattern. Supported by the presence of a nearby mountain range, this pattern suggests that not only synoptic scales exert their influence on the boundary layer, but also mesoscale circulations. LES results show a satisfactory correspondence of the vertical structure of turbulent variables with observations. We also find that when large-scale advection and subsidence are included in the simulation, the values for turbulent kinetic energy are lower than without these large-scale forcings. We conclude that the prototypical CBL is a valid representation of the boundary-layer dynamics near regions characterized by complex topography and small-scale surface heterogeneity, provided that surface- and large-scale forcings are representative for the local boundary layer.

Posted on 24 April 2015 | 12:00 am


The decrease in mid-stratospheric tropical ozone since 1991

The decrease in mid-stratospheric tropical ozone since 1991

Atmospheric Chemistry and Physics, 15, 4215-4224, 2015

Author(s): G. E. Nedoluha, D. E. Siskind, A. Lambert, and C. Boone

While global stratospheric O3 has begun to recover, there are localized regions where O3 has decreased since 1991. Specifically, we use measurements from the Halogen Occultation Experiment (HALOE) for the period 1991–2005 and the NASA Aura Microwave Limb Sounder (MLS) for the period 2004–2013 to demonstrate a significant decrease in O3 near ~ 10 hPa in the tropics. O3 in this region is very sensitive to variations in NOy, and the observed decrease can be understood as a spatially localized, yet long-term increase in NOy. In turn, using data from MLS and from the Atmospheric Chemistry Experiment (ACE), we show that the NOy variations are caused by decreases in N2O which are likely linked to long-term variations in dynamics. To illustrate how variations in dynamics can affect N2O and O3, we show that by decreasing the upwelling in the tropics, more of the N2O can photodissociate with a concomitant increase in NOy production (via N2O + O(1D) ? 2NO) at 10 hPa. Ultimately, this can cause an O3 decrease of the observed magnitude.

Posted on 23 April 2015 | 12:00 am


Vapor wall deposition in Teflon chambers

Vapor wall deposition in Teflon chambers

Atmospheric Chemistry and Physics, 15, 4197-4214, 2015

Author(s): X. Zhang, R. H. Schwantes, R. C. McVay, H. Lignell, M. M. Coggon, R. C. Flagan, and J. H. Seinfeld

Teflon chambers are ubiquitous in studies of atmospheric chemistry. Secondary organic aerosol (SOA) formation can be underestimated, owing to deposition of SOA-forming vapors to the chamber wall. We present here an experimental protocol and a model framework to constrain the vapor–wall interactions in Teflon chambers. We measured the wall deposition rates of 25 oxidized organic compounds generated from the photooxidation of isoprene, toluene, ?-pinene, and dodecane in two chambers that had been extensively used and in two new unused chambers. We found that the extent of prior use of the chamber did not significantly affect the sorption behavior of the Teflon films. Among the 25 compounds studied, the maximum wall deposition rate is exhibited by the most highly oxygenated and least volatile compounds. By optimizing the model output to the observed vapor decay profiles, we identified that the dominant parameter governing the extent of wall deposition of a compound is its wall accommodation coefficient (αwi), which can be correlated through its volatility with the number of carbons and oxygens in the molecule. By doing so, the wall-induced deposition rate of intermediate/semi-volatile organic vapors can be reasonably predicted based on their molecular constituency. The extent to which vapor wall deposition impacts measured SOA yields depends on the competition between uptake of organic vapors by suspended particles and the chamber wall. The timescale associated with vapor wall deposition can vary from minutes to hours depending on the value of αw,i. For volatile and intermediate volatility organic compounds (small αw,i), gas-particle partitioning will dominate wall deposition for typical particle number concentrations in chamber experiments. For compounds characterized by relatively large αw,i, vapor transport to particles is suppressed by competition with the chamber wall even with perfect particle accommodation.

Posted on 23 April 2015 | 12:00 am


Absorption of aerosols above clouds from POLDER/PARASOL measurements and estimation of their direct radiative effect

Absorption of aerosols above clouds from POLDER/PARASOL measurements and estimation of their direct radiative effect

Atmospheric Chemistry and Physics, 15, 4179-4196, 2015

Author(s): F. Peers, F. Waquet, C. Cornet, P. Dubuisson, F. Ducos, P. Goloub, F. Szczap, D. Tanré, and F. Thieuleux

This study presents an original method to evaluate key parameters for the estimation of the direct radiative effect (DRE) of aerosol above clouds: the absorption of the the cloud albedo. It is based on multi-angle total and polarized radiances both provided by the A-train satellite instrument POLDER – Polarization and Directionality of Earth Reflectances. The sensitivities brought by each kind of measurements are used in a complementary way. Polarization mostly translates scattering processes and is thus used to estimate scattering aerosol optical thickness and aerosol size. On the other hand, total radiances, together with the scattering properties of aerosols, are used to evaluate the absorption optical thickness of aerosols and cloud optical thickness. The retrieval of aerosol and clouds properties (i.e., aerosol and cloud optical thickness, aerosol single scattering albedo and Ångström exponent) is restricted to homogeneous and optically thick clouds (cloud optical thickness larger than 3). In addition, a procedure has been developed to process the shortwave DRE of aerosols above clouds. Three case studies have been selected: a case of absorbing biomass burning aerosols above clouds over the southeast Atlantic Ocean, a Siberian biomass burning event and a layer of Saharan dust above clouds off the northwest coast of Africa. Besides these case studies, both algorithms have been applied to the southeast Atlantic Ocean and the results have been averaged during August 2006. The mean DRE is found to be 33.5 W m?2 (warming). Finally, the effect of the heterogeneity of clouds has been investigated and reveals that it affects mostly the retrieval of the cloud optical thickness and not greatly the aerosols properties. The homogenous cloud assumption used in both the properties retrieval and the DRE processing leads to a slight underestimation of the DRE.

Posted on 22 April 2015 | 12:00 am


Single-particle characterization of ice-nucleating particles and ice particle residuals sampled by three different techniques

Single-particle characterization of ice-nucleating particles and ice particle residuals sampled by three different techniques

Atmospheric Chemistry and Physics, 15, 4161-4178, 2015

Author(s): A. Worringen, K. Kandler, N. Benker, T. Dirsch, S. Mertes, L. Schenk, U. Kästner, F. Frank, B. Nillius, U. Bundke, D. Rose, J. Curtius, P. Kupiszewski, E. Weingartner, P. Vochezer, J. Schneider, S. Schmidt, S. Weinbruch, and M. Ebert

In the present work, three different techniques to separate ice-nucleating particles (INPs) as well as ice particle residuals (IPRs) from non-ice-active particles are compared. The Ice Selective Inlet (ISI) and the Ice Counterflow Virtual Impactor (Ice-CVI) sample ice particles from mixed-phase clouds and allow after evaporation in the instrument for the analysis of the residuals. The Fast Ice Nucleus Chamber (FINCH) coupled with the Ice Nuclei Pumped Counterflow Virtual Impactor (IN-PCVI) provides ice-activating conditions to aerosol particles and extracts the activated particles for analysis. The instruments were run during a joint field campaign which took place in January and February 2013 at the High Alpine Research Station Jungfraujoch (Switzerland). INPs and IPRs were analyzed offline by scanning electron microscopy and energy-dispersive X-ray microanalysis to determine their size, chemical composition and mixing state. Online analysis of the size and chemical composition of INP activated in FINCH was performed by laser ablation mass spectrometry. With all three INP/IPR separation techniques high abundances (median 20–70%) of instrumental contamination artifacts were observed (ISI: Si-O spheres, probably calibration aerosol; Ice-CVI: Al-O particles; FINCH + IN-PCVI: steel particles). After removal of the instrumental contamination particles, silicates, Ca-rich particles, carbonaceous material and metal oxides were the major INP/IPR particle types obtained by all three techniques. In addition, considerable amounts (median abundance mostly a few percent) of soluble material (e.g., sea salt, sulfates) were observed. As these soluble particles are often not expected to act as INP/IPR, we consider them as potential measurement artifacts. Minor types of INP/IPR include soot and Pb-bearing particles. The Pb-bearing particles are mainly present as an internal mixture with other particle types. Most samples showed a maximum of the INP/IPR size distribution at 200–400 nm in geometric diameter. In a few cases, a second supermicron maximum was identified. Soot/carbonaceous material and metal oxides were present mainly in the sub-micrometer range. Silicates and Ca-rich particles were mainly found with diameters above 1 ?m (using ISI and FINCH), in contrast to the Ice-CVI which also sampled many submicron particles of both groups. Due to changing meteorological conditions, the INP/IPR composition was highly variable if different samples were compared. Thus, the observed discrepancies between the different separation techniques may partly result from the non-parallel sampling. The differences of the particle group relative number abundance as well as the mixing state of INP/IPR clearly demonstrate the need of further studies to better understand the influence of the separation techniques on the INP/IPR chemical composition. Also, it must be concluded that the abundance of contamination artifacts in the separated INP and IPR is generally large and should be corrected for, emphasizing the need for the accompanying chemical measurements. Thus, further work is needed to allow for routine operation of the three separation techniques investigated.

Posted on 22 April 2015 | 12:00 am


Elemental composition and clustering behaviour of ?-pinene oxidation products for different oxidation conditions

Elemental composition and clustering behaviour of ?-pinene oxidation products for different oxidation conditions

Atmospheric Chemistry and Physics, 15, 4145-4159, 2015

Author(s): A. P. Praplan, S. Schobesberger, F. Bianchi, M. P. Rissanen, M. Ehn, T. Jokinen, H. Junninen, A. Adamov, A. Amorim, J. Dommen, J. Duplissy, J. Hakala, A. Hansel, M. Heinritzi, J. Kangasluoma, J. Kirkby, M. Krapf, A. Kürten, K. Lehtipalo, F. Riccobono, L. Rondo, N. Sarnela, M. Simon, A. Tomé, J. Tröstl, P. M. Winkler, C. Williamson, P. Ye, J. Curtius, U. Baltensperger, N. M. Donahue, M. Kulmala, and D. R. Worsnop

This study presents the difference between oxidised organic compounds formed by ?-pinene oxidation under various conditions in the CLOUD environmental chamber: (1) pure ozonolysis (in the presence of hydrogen as hydroxyl radical (OH) scavenger) and (2) OH oxidation (initiated by nitrous acid (HONO) photolysis by ultraviolet light) in the absence of ozone.

We discuss results from three Atmospheric Pressure interface Time-of-Flight (APi-TOF) mass spectrometers measuring simultaneously the composition of naturally charged as well as neutral species (via chemical ionisation with nitrate). Natural chemical ionisation takes place in the CLOUD chamber and organic oxidised compounds form clusters with nitrate, bisulfate, bisulfate/sulfuric acid clusters, ammonium, and dimethylaminium, or get protonated. The results from this study show that this process is selective for various oxidised organic compounds with low molar mass and ions, so that in order to obtain a comprehensive picture of the elemental composition of oxidation products and their clustering behaviour, several instruments must be used. We compare oxidation products containing 10 and 20 carbon atoms and show that highly oxidised organic compounds are formed in the early stages of the oxidation.

Posted on 22 April 2015 | 12:00 am


Atmospheric transport simulations in support of the Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE)

Atmospheric transport simulations in support of the Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE)

Atmospheric Chemistry and Physics, 15, 4093-4116, 2015

Author(s): J. M. Henderson, J. Eluszkiewicz, M. E. Mountain, T. Nehrkorn, R. Y.-W. Chang, A. Karion, J. B. Miller, C. Sweeney, N. Steiner, S. C. Wofsy, and C. E. Miller

This paper describes the atmospheric modeling that underlies the Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) science analysis, including its meteorological and atmospheric transport components (polar variant of the Weather Research and Forecasting (WRF) and Stochastic Time Inverted Lagrangian Transport (STILT) models), and provides WRF validation for May–October 2012 and March–November 2013 – the first 2 years of the aircraft field campaign. A triply nested computational domain for WRF was chosen so that the innermost domain with 3.3 km grid spacing encompasses the entire mainland of Alaska and enables the substantial orography of the state to be represented by the underlying high-resolution topographic input field. Summary statistics of the WRF model performance on the 3.3 km grid indicate good overall agreement with quality-controlled surface and radiosonde observations. Two-meter temperatures are generally too cold by approximately 1.4 K in 2012 and 1.1 K in 2013, while 2 m dewpoint temperatures are too low (dry) by 0.2 K in 2012 and too high (moist) by 0.6 K in 2013. Wind speeds are biased too low by 0.2 m s?1 in 2012 and 0.3 m s?1 in 2013. Model representation of upper level variables is very good. These measures are comparable to model performance metrics of similar model configurations found in the literature. The high quality of these fine-resolution WRF meteorological fields inspires confidence in their use to drive STILT for the purpose of computing surface influences ("footprints") at commensurably increased resolution. Indeed, footprints generated on a 0.1° grid show increased spatial detail compared with those on the more common 0.5° grid, better allowing for convolution with flux models for carbon dioxide and methane across the heterogeneous Alaskan landscape. Ozone deposition rates computed using STILT footprints indicate good agreement with observations and exhibit realistic seasonal variability, further indicating that WRF-STILT footprints are of high quality and will support accurate estimates of CO2 and CH4 surface–atmosphere fluxes using CARVE observations.

Posted on 21 April 2015 | 12:00 am


Characteristics of trace metals in traffic-derived particles in Hsuehshan Tunnel, Taiwan: size distribution, potential source, and fingerprinting metal ratio

Characteristics of trace metals in traffic-derived particles in Hsuehshan Tunnel, Taiwan: size distribution, potential source, and fingerprinting metal ratio

Atmospheric Chemistry and Physics, 15, 4117-4130, 2015

Author(s): Y.-C. Lin, C.-J. Tsai, Y.-C. Wu, R. Zhang, K.-H. Chi, Y.-T. Huang, S.-H. Lin, and S.-C. Hsu

Traffic emissions are a significant source of airborne particulate matter (PM) in ambient environments. These emissions contain an abundance of toxic metals and thus pose adverse effects on human health. Size-fractionated aerosol samples were collected from May to September 2013 by using micro-orifice uniform deposited impactors (MOUDIs). Sample collection was conducted simultaneously at the inlet and outlet sites of Hsuehshan Tunnel in northern Taiwan, which is the second-longest freeway tunnel (12.9 km) in Asia. This endeavor aims to characterize the chemical constituents and size distributions, as well as fingerprinting ratios of particulate metals emitted by vehicle fleets. A total of 36 metals in size-resolved aerosols were determined through inductively coupled plasma mass spectrometry. Three major groups – namely, tailpipe emissions (Zn, Pb, and V in fine mode), wear debris (Cu, Cd, Fe, Ga, Mn, Mo, Sb, and Sn), and resuspended dust (Ca, Mg, K, and Rb) – of airborne PM metals were categorized on the basis of the results of enrichment factor, correlation matrix, and principal component analysis. Size distributions of wear-originated metals resembled the pattern of crustal elements, which were predominated by super-micron particulates (PM1–10). By contrast, tailpipe exhaust elements such as Zn, Pb, and V were distributed mainly in submicron particles. By employing Cu as a tracer of wear abrasion, several inter-metal ratios – including Fe / Cu (14), Ba / Cu (1.05), Sb / Cu (0.16), Sn / Cu (0.10), and Ga / Cu (0.03) – served as fingerprints for wear debris. However, the data set collected in this work is useful for further studies on traffic emission inventory and human health effects of traffic-related PM.

Posted on 21 April 2015 | 12:00 am


Ice nucleation by water-soluble macromolecules

Ice nucleation by water-soluble macromolecules

Atmospheric Chemistry and Physics, 15, 4077-4091, 2015

Author(s): B. G. Pummer, C. Budke, S. Augustin-Bauditz, D. Niedermeier, L. Felgitsch, C. J. Kampf, R. G. Huber, K. R. Liedl, T. Loerting, T. Moschen, M. Schauperl, M. Tollinger, C. E. Morris, H. Wex, H. Grothe, U. Pöschl, T. Koop, and J. Fröhlich-Nowoisky

Cloud glaciation is critically important for the global radiation budget (albedo) and for initiation of precipitation. But the freezing of pure water droplets requires cooling to temperatures as low as 235 K. Freezing at higher temperatures requires the presence of an ice nucleator, which serves as a template for arranging water molecules in an ice-like manner. It is often assumed that these ice nucleators have to be insoluble particles. We point out that also free macromolecules which are dissolved in water can efficiently induce ice nucleation: the size of such ice nucleating macromolecules (INMs) is in the range of nanometers, corresponding to the size of the critical ice embryo. As the latter is temperature-dependent, we see a correlation between the size of INMs and the ice nucleation temperature as predicted by classical nucleation theory. Different types of INMs have been found in a wide range of biological species and comprise a variety of chemical structures including proteins, saccharides, and lipids. Our investigation of the fungal species Acremonium implicatum, Isaria farinosa, and Mortierella alpina shows that their ice nucleation activity is caused by proteinaceous water-soluble INMs. We combine these new results and literature data on INMs from fungi, bacteria, and pollen with theoretical calculations to develop a chemical interpretation of ice nucleation and water-soluble INMs. This has atmospheric implications since many of these INMs can be released by fragmentation of the carrier cell and subsequently may be distributed independently. Up to now, this process has not been accounted for in atmospheric models.

Posted on 21 April 2015 | 12:00 am


Analysis of actinic flux profiles measured from an ozonesonde balloon

Analysis of actinic flux profiles measured from an ozonesonde balloon

Atmospheric Chemistry and Physics, 15, 4131-4144, 2015

Author(s): P. Wang, M. Allaart, W. H. Knap, and P. Stammes

A green light sensor has been developed at KNMI to measure actinic flux profiles using an ozonesonde balloon. In total, 63 launches with ascending and descending profiles were performed between 2006 and 2010. The measured uncalibrated actinic flux profiles are analysed using the Doubling–Adding KNMI (DAK) radiative transfer model. Values of the cloud optical thickness (COT) along the flight track were taken from the Spinning Enhanced Visible and Infrared Imager (SEVIRI) Cloud Physical Properties (CPP) product. The impact of clouds on the actinic flux profile is evaluated on the basis of the cloud modification factor (CMF) at the cloud top and cloud base, which is the ratio between the actinic fluxes for cloudy and clear-sky scenes. The impact of clouds on the actinic flux is clearly detected: the largest enhancement occurs at the cloud top due to multiple scattering. The actinic flux decreases almost linearly from cloud top to cloud base. Above the cloud top the actinic flux also increases compared to clear-sky scenes. We find that clouds can increase the actinic flux to 2.3 times the clear-sky value at cloud top and decrease it to about 0.05 at cloud base. The relationship between CMF and COT agrees well with DAK simulations, except for a few outliers. Good agreement is found between the DAK-simulated actinic flux profiles and the observations for single-layer clouds in fully overcast scenes. The instrument is suitable for operational balloon measurements because of its simplicity and low cost. It is worth further developing the instrument and launching it together with atmospheric chemistry composition sensors.

Posted on 21 April 2015 | 12:00 am


On the derivation of particle nucleation rates from experimental formation rates

On the derivation of particle nucleation rates from experimental formation rates

Atmospheric Chemistry and Physics, 15, 4063-4075, 2015

Author(s): A. Kürten, C. Williamson, J. Almeida, J. Kirkby, and J. Curtius

Particle formation rates are usually measured at sizes larger than the critical size at which nucleation occurs. Due to loss of particles during their growth to the detection threshold, the measured formation rate is often substantially lower than the nucleation rate. For this reason a correction needs to be applied in order to determine the nucleation rate from the measured formation rate. Analytical formulae for the correction factor are provided in the literature. However, these methods were derived for atmospheric nucleation measurements and therefore need to be adjusted in order to be applied to chamber nucleation studies. Here we propose an alternative, numerical method that allows precise nucleation rates to be determined in arbitrary experimental environments. The method requires knowledge of the particle size distribution above detection threshold, the particle growth rate, and the particle loss rates as a function of particle size. The effect of self-coagulation, i.e., cluster–cluster collisions, is taken into account in the method.

Posted on 17 April 2015 | 12:00 am


Aerosol optical hygroscopicity measurements during the 2010 CARES campaign

Aerosol optical hygroscopicity measurements during the 2010 CARES campaign

Atmospheric Chemistry and Physics, 15, 4045-4061, 2015

Author(s): D. B. Atkinson, J. G. Radney, J. Lum, K. R. Kolesar, D. J. Cziczo, M. S. Pekour, Q. Zhang, A. Setyan, A. Zelenyuk, and C. D. Cappa

Measurements of the effect of water uptake on particulate light extinction or scattering made at two locations during the 2010 Carbonaceous Aerosols and Radiative Effects Study (CARES) study around Sacramento, CA are reported. The observed influence of water uptake, characterized through the dimensionless optical hygroscopicity parameter ?, is compared with calculations constrained by observed particle size distributions and size-dependent particle composition. A closure assessment has been carried out that allowed for determination of the average hygroscopic growth factors (GFs) at 85% relative humidity and the dimensionless hygroscopicity parameter κ for oxygenated organic aerosol (OA) and for supermicron particles (defined here as particles with aerodynamic diameters between 1 and 2.5 microns), yielding ? = 0.1–0.15 and 0.9–1.0, respectively. The derived range of oxygenated OA κ values are in line with previous observations. The relatively large values for supermicron particles is consistent with substantial contributions of sea-salt-containing particles in this size range. Analysis of time-dependent variations in the supermicron particle hygroscopicity suggest that atmospheric processing, specifically chloride displacement by nitrate and the accumulation of secondary organics on supermicron particles, can lead to substantial depression of the observed GF.

Posted on 17 April 2015 | 12:00 am


Corrigendum to "Photosensitised heterogeneous oxidation kinetics of biomass burning aerosol surrogates by ozone using an irradiated rectangular channel flow reactor" published in Atmos. Chem. Phys., 13, 6507–6522, 2013

Corrigendum to "Photosensitised heterogeneous oxidation kinetics of biomass burning aerosol surrogates by ozone using an irradiated rectangular channel flow reactor" published in Atmos. Chem. Phys., 13, 6507–6522, 2013

Atmospheric Chemistry and Physics, 15, 4043-4043, 2015

Author(s): S. M. Forrester and D. A. Knopf

No abstract available.

Posted on 17 April 2015 | 12:00 am


Trends and drivers of ozone human health and vegetation impact metrics from UK EMEP supersite measurements (1990–2013)

Trends and drivers of ozone human health and vegetation impact metrics from UK EMEP supersite measurements (1990–2013)

Atmospheric Chemistry and Physics, 15, 4025-4042, 2015

Author(s): C. S. Malley, M. R. Heal, G. Mills, and C. F. Braban

Analyses have been undertaken of the spatial and temporal trends and drivers of the distributions of ground-level O3 concentrations associated with potential impacts on human health and vegetation using measurements at the two UK European Monitoring and Evaluation Program (EMEP) supersites of Harwell and Auchencorth. These two sites provide representation of rural O3 over the wider geographic areas of south-east England and northern UK respectively. The O3 exposures associated with health and vegetation impacts were quantified respectively by the SOMO10 and SOMO35 metrics and by the flux-based PODY metrics for wheat, potato, beech and Scots pine. Statistical analyses of measured O3 and NOx concentrations were supplemented by analyses of meteorological data and NOx emissions along air-mass back trajectories.

The findings highlight the differing responses of impact metrics to the decreasing contribution of regional O3 episodes in determining O3 concentrations at Harwell between 1990 and 2013, associated with European NOx emission reductions. An improvement in human health-relevant O3 exposure observed when calculated by SOMO35, which decreased significantly, was not observed when quantified by SOMO10. The decrease in SOMO35 is driven by decreases in regionally produced O3 which makes a larger contribution to SOMO35 than to SOMO10. For the O3 vegetation impacts at Harwell, no significant trend was observed for the PODY metrics of the four species, in contrast to the decreasing trend in vegetation-relevant O3 exposure perceived when calculated using the crop AOT40 metric. The decreases in regional O3 production have not decreased PODY as climatic and plant conditions reduced stomatal conductance and uptake of O3 during regional O3 production.

Ozone concentrations at Auchencorth (2007–2013) were more influenced by hemispheric background concentrations than at Harwell. For health-related O3 exposures this resulted in lower SOMO35 but similar SOMO10 compared with Harwell; for vegetation PODY values, this resulted in greater impacts at Auchencorth for vegetation types with lower exceedance ("Y") thresholds and longer growing seasons (i.e. beech and Scots pine). Additionally, during periods influenced by regional O3 production, a greater prevalence of plant conditions which enhance O3 uptake (such as higher soil water potential) at Auchencorth compared to Harwell resulted in exacerbation of vegetation impacts at Auchencorth, despite being further from O3 precursor emission sources.

These analyses indicate that quantifications of future improvement in health-relevant O3 exposure achievable from pan-European O3 mitigation strategies are highly dependent on the choice of O3 concentration cut-off threshold, and reduction in potential health impact associated with more modest O3 concentrations requires reductions in O3 precursors on a larger (hemispheric) spatial scale. Additionally, while further reduction in regional O3 is more likely to decrease O3 vegetation impacts within the spatial domain of Auchencorth compared to Harwell, larger reductions in vegetation impact could be achieved across the UK from reduction of hemispheric background O3 concentrations.

Posted on 16 April 2015 | 12:00 am


The MACC-II 2007–2008 reanalysis: atmospheric dust evaluation and characterization over northern Africa and the Middle East

The MACC-II 2007–2008 reanalysis: atmospheric dust evaluation and characterization over northern Africa and the Middle East

Atmospheric Chemistry and Physics, 15, 3991-4024, 2015

Author(s): E. Cuevas, C. Camino, A. Benedetti, S. Basart, E. Terradellas, J. M. Baldasano, J. J. Morcrette, B. Marticorena, P. Goloub, A. Mortier, A. Berjón, Y. Hernández, M. Gil-Ojeda, and M. Schulz

In the present work, atmospheric mineral dust from a MACC-II short reanalysis run for 2 years (2007–2008) has been evaluated over northern Africa and the Middle East using satellite aerosol products (from MISR, MODIS and OMI satellite sensors), ground-based AERONET data, in situ PM10 concentrations from AMMA, and extinction vertical profiles from two ground-based lidars and CALIOP satellite-based lidar. The MACC-II aerosol optical depth (AOD) spatial and temporal (seasonal and interannual) variability shows good agreement with those provided by satellite sensors. The capability of the model to reproduce the AOD, Ångström exponent (AE) and dust optical depth (DOD) from daily to seasonal time-scale is quantified over 26 AERONET stations located in eight geographically distinct regions by using statistical parameters. Overall DOD seasonal variation is fairly well simulated by MACC-II in all regions, although the correlation is significantly higher in dust transport regions than in dust source regions. The ability of MACC-II in reproducing dust vertical profiles has been assessed by comparing seasonal averaged extinction vertical profiles simulated by MACC-II under dust conditions with corresponding extinction profiles obtained with lidar instruments at M'Bour and Santa Cruz de Tenerife, and with CALIOP. We find a good agreement in dust layers structures and averaged extinction vertical profiles between MACC-II, the lidars and CALIOP above the marine boundary layer from 1 to 6 km. Surface dust daily mean concentrations from MACC-II reanalysis has been evaluated with daily averaged PM10 at three monitoring stations of the Sahelian Dust Transect. MACC-II correctly reproduces daily to interannual surface dust concentration variability, although it underestimates daily and monthly means all year long, especially in winter and early spring (dry season). MACC-II reproduces well the dust variability recorded along the station transect which reflects the variability in dust emission by different Saharan sources, but fails in reproducing the sporadic and very strong dust events associated to mesoscale convective systems during the wet season.

Posted on 16 April 2015 | 12:00 am


Evaluation of the GEM-AQ model in the context of the AQMEII Phase 1 project

Evaluation of the GEM-AQ model in the context of the AQMEII Phase 1 project

Atmospheric Chemistry and Physics, 15, 3971-3990, 2015

Author(s): J. Struzewska, M. Zdunek, J. W. Kaminski, L. ?obocki, M. Porebska, M. Jefimow, and L. Gawuc

In the scope of the AQMEII Phase 1 project the GEM-AQ model was run over Europe for the year 2006. The modelling domain was defined using a global variable resolution grid with a rotated equator and uniform resolution of 0.2° × 0.2° over the European continent. Spatial distribution and temporal variability of the GEM-AQ model results were analysed for surface ozone and PM10 concentrations. Model results were compared with measurements available in the ENSEMBLE database. Statistical measures were used to evaluate performance of the GEM-AQ model. The mean bias error, the mean absolute gross error and the Pearson correlation coefficient were calculated for the maximum 8 h running average ozone concentrations and daily mean PM10 concentrations. The GEM-AQ model performance was characterized for station types, European climatic regions and seasons. The best performance for ozone was obtained at suburban stations, and the worst performance was obtained for rural stations where the model tends to underestimate. The best results for PM10 were calculated for urban stations, while over most of Europe concentrations at rural sites were too high. Discrepancies between modelled and observed concentrations were discussed in the context of emission data uncertainty as well as the impact of large-scale dynamics and circulation of air masses. Presented analyses suggest that interpretation of modelling results is enhanced when regional climate characteristics are taken into consideration.

Posted on 16 April 2015 | 12:00 am


Radiative forcing and climate metrics for ozone precursor emissions: the impact of multi-model averaging

Radiative forcing and climate metrics for ozone precursor emissions: the impact of multi-model averaging

Atmospheric Chemistry and Physics, 15, 3957-3969, 2015

Author(s): C. R. MacIntosh, K. P. Shine, and W. J. Collins

Multi-model ensembles are frequently used to assess understanding of the response of ozone and methane lifetime to changes in emissions of ozone precursors such as NOx, VOCs (volatile organic compounds) and CO. When these ozone changes are used to calculate radiative forcing (RF) (and climate metrics such as the global warming potential (GWP) and global temperature-change potential (GTP)) there is a methodological choice, determined partly by the available computing resources, as to whether the mean ozone (and methane) concentration changes are input to the radiation code, or whether each model's ozone and methane changes are used as input, with the average RF computed from the individual model RFs. We use data from the Task Force on Hemispheric Transport of Air Pollution source–receptor global chemical transport model ensemble to assess the impact of this choice for emission changes in four regions (East Asia, Europe, North America and South Asia).

We conclude that using the multi-model mean ozone and methane responses is accurate for calculating the mean RF, with differences up to 0.6% for CO, 0.7% for VOCs and 2% for NOx. Differences of up to 60% for NOx 7% for VOCs and 3% for CO are introduced into the 20 year GWP. The differences for the 20 year GTP are smaller than for the GWP for NOx, and similar for the other species.

However, estimates of the standard deviation calculated from the ensemble-mean input fields (where the standard deviation at each point on the model grid is added to or subtracted from the mean field) are almost always substantially larger in RF, GWP and GTP metrics than the true standard deviation, and can be larger than the model range for short-lived ozone RF, and for the 20 and 100 year GWP and 100 year GTP. The order of averaging has most impact on the metrics for NOx, as the net values for these quantities is the residual of the sum of terms of opposing signs. For example, the standard deviation for the 20 year GWP is 2–3 times larger using the ensemble-mean fields than using the individual models to calculate the RF. The source of this effect is largely due to the construction of the input ozone fields, which overestimate the true ensemble spread.

Hence, while the average of multi-model fields are normally appropriate for calculating mean RF, GWP and GTP, they are not a reliable method for calculating the uncertainty in these fields, and in general overestimate the uncertainty.

Posted on 15 April 2015 | 12:00 am


Dimensions and aspect ratios of natural ice crystals

Dimensions and aspect ratios of natural ice crystals

Atmospheric Chemistry and Physics, 15, 3933-3956, 2015

Author(s): J. Um, G. M. McFarquhar, Y. P. Hong, S.-S. Lee, C. H. Jung, R. P. Lawson, and Q. Mo

During the 2006 Tropical Warm Pool International Cloud Experiment (TWP-ICE) in the tropics, the 2008 Indirect and Semi-Direct Aerosol Campaign (ISDAC) in the Arctic, and the 2010 Small PARTicles In CirrUS (SPARTICUS) campaign at mid-latitudes, high-resolution images of ice crystals were recorded by a Cloud Particle Imager at temperatures (T) between ?87 and 0 °C. The projected maximum dimension (D'), length (L'), and width (W') of pristine columns, plates, and component bullets of bullet rosettes were measured using newly developed software, the Ice Crystal Ruler. The number of bullets in each bullet rosette was also measured. Column crystals were further distinguished as either horizontally oriented columns or columns with other orientations to eliminate any orientation effect on the measured dimensions. The dimensions and aspect ratios (AR, the dimension of the major axis divided by the dimension of the minor axis) of crystals were determined as functions of temperature, geophysical location, and type of cirrus.

Dimensions of crystals generally increased with temperature. Columns and bullets had larger dimensions (i.e., W') of the minor axis (i.e., a axis) for a given dimension (i.e., D' orL') of the major axis (i.e., c axis), and thus smaller AR, as T increased, whereas this trend did not occur for plate crystals. The average number of branches in bullet rosettes was 5.50 ± 1.35 during three campaigns and 6.32 ± 1.34 (5.46 ± 1.34; 4.95 ± 1.01) during TWP-ICE (SPARTICUS; ISDAC). The AR of bullets increased with the number of branches in bullet rosettes. Most dimensions of crystals and ARs of columnar crystals measured during SPARTICUS were larger than those measured during TWP-ICE and ISDAC at −67 < T < -35 °C and at −40 < T < −15 °C, respectively. The relative occurrence of varying pristine habits depended strongly on cirrus type (i.e., anvil or non-anvil clouds), with plates especially occurring more frequently in anvils. The LW relationships of columns derived using current data exhibited a strong dependence on temperature; similar relationships determined in previous studies were within the range of the current data.

Posted on 15 April 2015 | 12:00 am


Simulations of atmospheric OH, O3 and NO3 reactivities within and above the boreal forest

Simulations of atmospheric OH, O3 and NO3 reactivities within and above the boreal forest

Atmospheric Chemistry and Physics, 15, 3909-3932, 2015

Author(s): D. Mogensen, R. Gierens, J. N. Crowley, P. Keronen, S. Smolander, A. Sogachev, A. C. Nölscher, L. Zhou, M. Kulmala, M. J. Tang, J. Williams, and M. Boy

Using the 1-D atmospheric chemistry transport model SOSAA, we have investigated the atmospheric reactivity of a boreal forest ecosystem during the HUMPPA-COPEC-10 campaign (summer 2010, at SMEAR~II in southern Finland). For the very first time, we present vertically resolved model simulations of the NO3 and O3 reactivity (R) together with the modelled and measured reactivity of OH. We find that OH is the most reactive oxidant (R ∼ 3 s-1) followed by NO3 (R ∼ 0.07 s-1) and O3 (R ∼ 2 × 10-5s-1). The missing OH reactivity was found to be large in accordance with measurements (∼ 65%) as would be expected from the chemical subset described in the model. The accounted OH radical sinks were inorganic compounds (∼ 41%, mainly due to reaction with CO), emitted monoterpenes (∼ 14%) and oxidised biogenic volatile organic compounds (∼ 44%). The missing reactivity is expected to be due to unknown biogenic volatile organic compounds and their photoproducts, indicating that the true main sink of OH is not expected to be inorganic compounds. The NO3 radical was found to react mainly with primary emitted monoterpenes (∼ 60%) and inorganic compounds (∼ 37%, including NO2). NO2 is, however, only a temporary sink of NO3 under the conditions of the campaign (with typical temperatures of 20–25 °C) and does not affect the NO3 concentration. We discuss the difference between instantaneous and steady-state reactivity and present the first boreal forest steady-state lifetime of NO3 (113 s). O3 almost exclusively reacts with inorganic compounds (∼ 91%, mainly NO, but also NO2 during night) and less with primary emitted sesquiterpenes (∼ 6%) and monoterpenes (∼ 3%). When considering the concentration of the oxidants investigated, we find that OH is the oxidant that is capable of removing organic compounds at a faster rate during daytime, whereas NO3 can remove organic molecules at a faster rate during night-time. O3 competes with OH and NO3 during a short period of time in the early morning (around 5 a.m. local time) and in the evening (around 7–8 p.m.). As part of this study, we developed a simple empirical parameterisation for conversion of measured spectral irradiance into actinic flux. Further, the meteorological conditions were evaluated using radiosonde observations and ground-based measurements. The overall vertical structure of the boundary layer is discussed, together with validation of the surface energy balance and turbulent fluxes. The sensible heat and momentum fluxes above the canopy were on average overestimated, while the latent heat flux was underestimated.

Posted on 15 April 2015 | 12:00 am


Spatial and temporal variation in CO over Alberta using measurements from satellites, aircraft, and ground stations

Spatial and temporal variation in CO over Alberta using measurements from satellites, aircraft, and ground stations

Atmospheric Chemistry and Physics, 15, 3893-3908, 2015

Author(s): H. S. Marey, Z. Hashisho, L. Fu, and J. Gille

Alberta is Canada's largest oil producer, and its oil sands deposits comprise 30% of the world's oil reserves. The process of bitumen extraction and upgrading releases trace gases and aerosols to the atmosphere. In this study we present satellite-based analysis to explore, for the first time, various contributing factors that affect tropospheric carbon monoxide (CO) levels over Alberta. The multispectral product that uses both near-infrared (NIR) and the thermal-infrared (TIR) radiances for CO retrieval from the Measurements of Pollution in the Troposphere (MOPITT) is examined for the 12-year period from 2002 to 2013. The Moderate Resolution Imaging Spectroradiometer (MODIS) thermal anomaly product from 2001 to 2013 is employed to investigate the seasonal and temporal variations in forest fires. Additionally, in situ CO measurements at industrial and urban sites are compared to satellite data. Furthermore, the available MOZAIC/IAGOS (Measurement of Ozone, Water Vapor, Carbon Monoxide, Nitrogen Oxide by Airbus In-Service Aircraft/In service Aircraft for Global Observing System) aircraft CO profiles (April 2009–December 2011) are used to validate MOPITT CO data. The climatological time curtain plot and spatial maps for CO over northern Alberta indicate the signatures of transported CO for two distinct biomass burning seasons: summer and spring. Distinct seasonal patterns of CO at the urban sites (Edmonton and Calgary) point to the strong influence of traffic. Meteorological parameters play an important role in the CO spatial distribution at various pressure levels. Northern Alberta shows a stronger upward lifting motion which leads to larger CO total column values, while the poor dispersion in central and southern Alberta exacerbates the surface CO pollution. Interannual variations in satellite data depict a slightly decreasing trend for both regions, while the decline trend is more evident from ground observations, especially at the urban sites. MOPITT CO vertical averages and MOZAIC/IAGOS aircraft profiles were in good agreement within the standard deviations at all pressure levels. There is consistency between the time evolution of high-CO episodes monitored by satellite and ground measurements and the fire frequency peak time, which implies that biomass burning has affected the tropospheric CO distribution in northern Alberta. These findings have further demonstrated the potential use of the MOPITT V5 multispectral (NIR + TIR) product for assessing a complicated surface process.

Posted on 14 April 2015 | 12:00 am


Comparisons of polar processing diagnostics from 34 years of the ERA-Interim and MERRA reanalyses

Comparisons of polar processing diagnostics from 34 years of the ERA-Interim and MERRA reanalyses

Atmospheric Chemistry and Physics, 15, 3873-3892, 2015

Author(s): Z. D. Lawrence, G. L. Manney, K. Minschwaner, M. L. Santee, and A. Lambert

We present a comprehensive comparison of polar processing diagnostics derived from the National Aeronautics and Space Administration (NASA) Modern Era Retrospective-analysis for Research and Applications (MERRA) and the European Centre for Medium-Range Weather Forecasts (ECMWF) Interim Reanalysis (ERA-Interim). We use diagnostics that focus on meteorological conditions related to stratospheric chemical ozone loss based on temperatures, polar vortex dynamics, and air parcel trajectories to evaluate the effects these reanalyses might have on polar processing studies. Our results show that the agreement between MERRA and ERA-Interim changes significantly over the 34 years from 1979 to 2013 in both hemispheres and in many cases improves. By comparing our diagnostics during five time periods when an increasing number of higher-quality observations were brought into these reanalyses, we show how changes in the data assimilation systems (DAS) of MERRA and ERA-Interim affected their meteorological data. Many of our stratospheric temperature diagnostics show a convergence toward significantly better agreement, in both hemispheres, after 2001 when Aqua and GOES (Geostationary Operational Environmental Satellite) radiances were introduced into the DAS. Other diagnostics, such as the winter mean volume of air with temperatures below polar stratospheric cloud formation thresholds (VPSC) and some diagnostics of polar vortex size and strength, do not show improved agreement between the two reanalyses in recent years when data inputs into the DAS were more comprehensive. The polar processing diagnostics calculated from MERRA and ERA-Interim agree much better than those calculated from earlier reanalysis data sets. We still, however, see fairly large differences in many of the diagnostics in years prior to 2002, raising the possibility that the choice of one reanalysis over another could significantly influence the results of polar processing studies. After 2002, we see overall good agreement among the diagnostics, which demonstrates that the ERA-Interim and MERRA reanalyses are equally appropriate choices for polar processing studies of recent Arctic and Antarctic winters.

Posted on 13 April 2015 | 12:00 am


Determination of interfacial parameters of a soluble particle in a nonideal solution from measured deliquescence and efflorescence humidities

Determination of interfacial parameters of a soluble particle in a nonideal solution from measured deliquescence and efflorescence humidities

Atmospheric Chemistry and Physics, 15, 3851-3871, 2015

Author(s): O. Hellmuth and A. K. Shchekin

In order to study the growth/shrinking of a hygroscopic nanoparticle during hydration/dehydration in an atmosphere of water vapour, we have employed a thermodynamic approach proposed by Shchekin et al. (2008). This approach uses the mechanic and thermodynamic concept of disjoining pressure of thin films and allows, among others, the prediction of the humidity growth factor of both (i) a homogeneous solution droplet with completely dissolved residual core and (ii) a heterogeneous solution droplet with partially dissolved residual core as a function of the ambient relative humidity. For application to a nanometric sodium chloride particle we have extended the original approach by (i) considering the nonideality of the solution through the dependence of molecular volumes of the solvent and solute molecules and the solute and solvent activities on the solution concentration, (ii) deriving an equation for the estimation of the efflorescence properties of a homogeneous solution droplet, and (iii) combining the empirical power law fittings for the size dependence of the deliquescence and efflorescence relative humidity values by Biskos et al. (2006a). It was demonstrated how the solution/solute interface energy and the correlation length of a thin solution film can be determined from a combination of experimentally determinable efflorescence and deliquescence humidities with the present calculus. The solution/solute interface energy was found to be in close agreement with some previous values reported in the literature, while it strongly differs from data of some other sources. The calculated deliquescence humidity shows a low sensitivity to the choice of the numerical value for the film correlation length. The estimated film correlation length of 1 nm for a nanometric sodium chloride particle with dry particle radius of 5 nm was found to be reconcilable with available a priori estimates of the correlation length from the literature when the measurement uncertainty of the deliquescence humidity is considered. Considering the combination of an extensive calculus, a comprehensive set of thermophysical constraints, and independent measurements of the deliquescence and efflorescence humidities as functions of dry particle radius, the obtained values of the solution/solute interface energy and the correlation length are in close agreement with previous estimations. The humidification of sodium chloride particles in the initial hydration stages was found to be very sensitive to the specification of the disjoining pressure. The enhancement of the wettability of the particle surface leads to an earlier onset of hygroscopic growth.

Posted on 10 April 2015 | 12:00 am


Transport of anthropogenic and biomass burning aerosols from Europe to the Arctic during spring 2008

Transport of anthropogenic and biomass burning aerosols from Europe to the Arctic during spring 2008

Atmospheric Chemistry and Physics, 15, 3831-3850, 2015

Author(s): L. Marelle, J.-C. Raut, J. L. Thomas, K. S. Law, B. Quennehen, G. Ancellet, J. Pelon, A. Schwarzenboeck, and J. D. Fast

During the POLARCAT-France airborne campaign in April 2008, pollution originating from anthropogenic and biomass burning emissions was measured in the European Arctic. We compare these aircraft measurements with simulations using the WRF-Chem model to investigate model representation of aerosols transported from Europe to the Arctic. Modeled PM2.5 is evaluated using European Monitoring and Evaluation Programme (EMEP) measurements in source regions and POLARCAT aircraft measurements in the Scandinavian Arctic. Total PM2.5 agrees well with the measurements, although the model overestimates nitrate and underestimates organic carbon in source regions. Using WRF-Chem in combination with the Lagrangian model FLEXPART-WRF, we find that during the campaign the research aircraft sampled two different types of European plumes: mixed anthropogenic and fire plumes from eastern Europe and Russia transported below 2 km, and anthropogenic plumes from central Europe uplifted by warm conveyor belt circulations to 5–6 km. Both modeled plume types had undergone significant wet scavenging (> 50% PM10) during transport. Modeled aerosol vertical distributions and optical properties below the aircraft are evaluated in the Arctic using airborne lidar measurements. Model results show that the pollution event transported aerosols into the Arctic (> 66.6° N) for a 4-day period. During this 4-day period, biomass burning emissions have the strongest influence on concentrations between 2.5 and 3 km altitudes, while European anthropogenic emissions influence aerosols at both lower (~ 1.5 km) and higher altitudes (~ 4.5 km). As a proportion of PM2.5, modeled black carbon and SO4= concentrations are more enhanced near the surface in anthropogenic plumes. The European plumes sampled during the POLARCAT-France campaign were transported over the region of springtime snow cover in northern Scandinavia, where they had a significant local atmospheric warming effect. We find that, during this transport event, the average modeled top-of-atmosphere (TOA) shortwave direct and semi-direct radiative effect (DSRE) north of 60° N over snow and ice-covered surfaces reaches +0.58 W m−2, peaking at +3.3 W m−2 at noon over Scandinavia and Finland.

Posted on 10 April 2015 | 12:00 am


CCN activation of fumed silica aerosols mixed with soluble pollutants

CCN activation of fumed silica aerosols mixed with soluble pollutants

Atmospheric Chemistry and Physics, 15, 3815-3829, 2015

Author(s): M. Dalirian, H. Keskinen, L. Ahlm, A. Ylisirniö, S. Romakkaniemi, A. Laaksonen, A. Virtanen, and I. Riipinen

Particle–water interactions of completely soluble or insoluble particles are fairly well understood but less is known of aerosols consisting of mixtures of soluble and insoluble components. In this study, laboratory measurements were performed to investigate cloud condensation nuclei (CCN) activity of silica particles mixed with ammonium sulfate (a salt), sucrose (a sugar) and bovine serum albumin known as BSA (a protein). The agglomerated structure of the silica particles was investigated using measurements with a differential mobility analyser (DMA) and an aerosol particle mass analyser (APM). Based on these data, the particles were assumed to be compact agglomerates when studying their CCN activation capabilities. Furthermore, the critical supersaturations of particles consisting of pure and mixed soluble and insoluble compounds were explored using existing theoretical frameworks. These results showed that the CCN activation of single-component particles was in good agreement with Köhler- and adsorption theory based models when the agglomerated structure was accounted for. For mixed particles the CCN activation was governed by the soluble components, and the soluble fraction varied considerably with particle size for our wet-generated aerosols. Our results confirm the hypothesis that knowing the soluble fraction is the key parameter needed for describing the CCN activation of mixed aerosols, and highlight the importance of controlled coating techniques for acquiring a detailed understanding of the CCN activation of atmospheric insoluble particles mixed with soluble pollutants.

Posted on 9 April 2015 | 12:00 am


Revisiting Twomey's approximation for peak supersaturation

Revisiting Twomey's approximation for peak supersaturation

Atmospheric Chemistry and Physics, 15, 3803-3814, 2015

Author(s): B. J. Shipway

Twomey's seminal 1959 paper provided lower and upper bound approximations to the estimation of peak supersaturation within an updraft and thus provides the first closed expression for the number of nucleated cloud droplets. The form of this approximation is simple, but provides a surprisingly good estimate and has subsequently been employed in more sophisticated treatments of nucleation parametrization. In the current paper, we revisit the lower bound approximation of Twomey and make a small adjustment that can be used to obtain a more accurate calculation of peak supersaturation under all potential aerosol loadings and thermodynamic conditions. In order to make full use of this improved approximation, the underlying integro-differential equation for supersaturation evolution and the condition for calculating peak supersaturation are examined. A simple rearrangement of the algebra allows for an expression to be written down that can then be solved with a single lookup table with only one independent variable for an underlying lognormal aerosol population. While multimodal aerosol with N different dispersion characteristics requires 2N+1 inputs to calculate the activation fraction, only N of these one-dimensional lookup tables are needed. No additional information is required in the lookup table to deal with additional chemical, physical or thermodynamic properties. The resulting implementation provides a relatively simple, yet computationally cheap, physically based parametrization of droplet nucleation for use in climate and Numerical Weather Prediction models.

Posted on 9 April 2015 | 12:00 am


High-resolution observations of the near-surface wind field over an isolated mountain and in a steep river canyon

High-resolution observations of the near-surface wind field over an isolated mountain and in a steep river canyon

Atmospheric Chemistry and Physics, 15, 3785-3801, 2015

Author(s): B. W. Butler, N. S. Wagenbrenner, J. M. Forthofer, B. K. Lamb, K. S. Shannon, D. Finn, R. M. Eckman, K. Clawson, L. Bradshaw, P. Sopko, S. Beard, D. Jimenez, C. Wold, and M. Vosburgh

A number of numerical wind flow models have been developed for simulating wind flow at relatively fine spatial resolutions (e.g., ~ 100 m); however, there are very limited observational data available for evaluating these high-resolution models. This study presents high-resolution surface wind data sets collected from an isolated mountain and a steep river canyon. The wind data are presented in terms of four flow regimes: upslope, afternoon, downslope, and a synoptically driven regime. There were notable differences in the data collected from the two terrain types. For example, wind speeds on the isolated mountain increased with distance upslope during upslope flow, but generally decreased with distance upslope at the river canyon site during upslope flow. In a downslope flow, wind speed did not have a consistent trend with position on the isolated mountain, but generally increased with distance upslope at the river canyon site. The highest measured speeds occurred during the passage of frontal systems on the isolated mountain. Mountaintop winds were often twice as high as wind speeds measured on the surrounding plain. The highest speeds measured in the river canyon occurred during late morning hours and were from easterly down-canyon flows, presumably associated with surface pressure gradients induced by formation of a regional thermal trough to the west and high pressure to the east. Under periods of weak synoptic forcing, surface winds tended to be decoupled from large-scale flows, and under periods of strong synoptic forcing, variability in surface winds was sufficiently large due to terrain-induced mechanical effects (speed-up over ridges and decreased speeds on leeward sides of terrain obstacles) that a large-scale mean flow would not be representative of surface winds at most locations on or within the terrain feature. These findings suggest that traditional operational weather model (i.e., with numerical grid resolutions of around 4 km or larger) wind predictions are not likely to be good predictors of local near-surface winds on sub-grid scales in complex terrain. Measurement data can be found at http://www.firemodels.org/index.php/windninja-introduction/windninja-publications.

Posted on 8 April 2015 | 12:00 am


Atmospheric oxidation of isoprene and 1,3-butadiene: influence of aerosol acidity and relative humidity on secondary organic aerosol

Atmospheric oxidation of isoprene and 1,3-butadiene: influence of aerosol acidity and relative humidity on secondary organic aerosol

Atmospheric Chemistry and Physics, 15, 3773-3783, 2015

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

The effects of acidic seed aerosols on the formation of secondary organic aerosol (SOA) have been examined in a number of previous studies, several of which have observed strong linear correlations between the aerosol acidity (measured as nmol H+ m?3 air sample volume) and the percent change in secondary organic carbon (SOC). The measurements have used several precursor compounds representative of different classes of biogenic hydrocarbons including isoprene, monoterpenes, and sesquiterpenes. To date, isoprene has displayed the most pronounced increase in SOC, although few measurements have been conducted with anthropogenic hydrocarbons. In the present study, we examine several aspects of the effect of aerosol acidity on the secondary organic carbon formation from the photooxidation of 1,3-butadiene, and extend the previous analysis of isoprene. The photooxidation products measured in the absence and presence of acidic sulfate aerosols were generated either through photochemical oxidation of SO2 or by nebulizing mixtures of ammonium sulfate and sulfuric acid into a 14.5 m3 smog chamber system. The results showed that, like isoprene and ?-caryophyllene, 1,3-butadiene SOC yields linearly correlate with increasing acidic sulfate aerosol. The observed acid sensitivity of 0.11% SOC increase per nmol m?3 increase in H+ was approximately a factor of 3 less than that measured for isoprene. The results also showed that the aerosol yield decreased with increasing humidity for both isoprene and 1,3-butadiene, although to different degrees. Increasing the absolute humidity from 2 to 12 g m?3 reduced the 1,3-butadiene yield by 45% and the isoprene yield by 85%.

Posted on 8 April 2015 | 12:00 am


Monsoonal variations in aerosol optical properties and estimation of aerosol optical depth using ground-based meteorological and air quality data in Peninsular Malaysia

Monsoonal variations in aerosol optical properties and estimation of aerosol optical depth using ground-based meteorological and air quality data in Peninsular Malaysia

Atmospheric Chemistry and Physics, 15, 3755-3771, 2015

Author(s): F. Tan, H. S. Lim, K. Abdullah, T. L. Yoon, and B. Holben

Obtaining continuous aerosol-optical-depth (AOD) measurements is a difficult task due to the cloud-cover problem. With the main motivation of overcoming this problem, an AOD-predicting model is proposed. In this study, the optical properties of aerosols in Penang, Malaysia were analyzed for four monsoonal seasons (northeast monsoon, pre-monsoon, southwest monsoon, and post-monsoon) based on data from the AErosol RObotic NETwork (AERONET) from February 2012 to November 2013. The aerosol distribution patterns in Penang for each monsoonal period were quantitatively identified according to the scattering plots of the Ångström exponent against the AOD. A new empirical algorithm was proposed to predict the AOD data. Ground-based measurements (i.e., visibility and air pollutant index) were used in the model as predictor data to retrieve the missing AOD data from AERONET due to frequent cloud formation in the equatorial region. The model coefficients were determined through multiple regression analysis using selected data set from in situ data. The calibrated model coefficients have a coefficient of determination, R2, of 0.72. The predicted AOD of the model was generated based on these calibrated coefficients and compared against the measured data through standard statistical tests, yielding a R2 of 0.68 as validation accuracy. The error in weighted mean absolute percentage error (wMAPE) was less than 0.40% compared with the real data. The results revealed that the proposed model efficiently predicted the AOD data. Performance of our model was compared against selected LIDAR data to yield good correspondence. The predicted AOD can enhance measured short- and long-term AOD and provide supplementary information for climatological studies and monitoring aerosol variation.

Posted on 7 April 2015 | 12:00 am


Methane as a diagnostic tracer of changes in the Brewer–Dobson circulation of the stratosphere

Methane as a diagnostic tracer of changes in the Brewer–Dobson circulation of the stratosphere

Atmospheric Chemistry and Physics, 15, 3739-3754, 2015

Author(s): E. E. Remsberg

This study makes use of time series of methane (CH4) data from the Halogen Occultation Experiment (HALOE) to detect whether there were any statistically significant changes of the Brewer–Dobson circulation (BDC) within the stratosphere during 1992–2005. The HALOE CH4 profiles are in terms of mixing ratio versus pressure altitude and are binned into latitude zones within the Southern Hemisphere and the Northern Hemisphere. Their separate time series are then analyzed using multiple linear regression (MLR) techniques. The CH4 trend terms for the Northern Hemisphere are significant and positive at 10° N from 50 to 7 hPa and larger than the tropospheric CH4 trends of about 3% decade?1 from 20 to 7 hPa. At 60° N the trends are clearly negative from 20 to 7 hPa. Their combined trends indicate an acceleration of the BDC in the middle stratosphere of the Northern Hemisphere during those years, most likely due to changes from the effects of wave activity. No similar significant BDC acceleration is found for the Southern Hemisphere. Trends from HALOE H2O are analyzed for consistency. Their mutual trends with CH4 are anti-correlated qualitatively in the middle and upper stratosphere, where CH4 is chemically oxidized to H2O. Conversely, their mutual trends in the lower stratosphere are dominated by their trends upon entry to the tropical stratosphere. Time series residuals for CH4 in the lower mesosphere also exhibit structures that are anti-correlated in some instances with those of the tracer-like species HCl. Their occasional aperiodic structures indicate the effects of transport following episodic, wintertime wave activity. It is concluded that observed multi-year, zonally averaged distributions of CH4 can be used to diagnose major instances of wave-induced transport in the middle atmosphere and to detect changes in the stratospheric BDC.

Posted on 7 April 2015 | 12:00 am


Observations and comparisons of cloud microphysical properties in spring and summertime Arctic stratocumulus clouds during the ACCACIA campaign

Observations and comparisons of cloud microphysical properties in spring and summertime Arctic stratocumulus clouds during the ACCACIA campaign

Atmospheric Chemistry and Physics, 15, 3719-3737, 2015

Author(s): G. Lloyd, T. W. Choularton, K. N. Bower, J. Crosier, H. Jones, J. R. Dorsey, M. W. Gallagher, P. Connolly, A. C. R. Kirchgaessner, and T. Lachlan-Cope

Measurements from four case studies in spring and summer-time Arctic stratocumulus clouds during the Aerosol-Cloud Coupling And Climate Interactions in the Arctic (ACCACIA) campaign are presented. We compare microphysics observations between cases and with previous measurements made in the Arctic and Antarctic. During ACCACIA, stratocumulus clouds were observed to consist of liquid at cloud tops, often at distinct temperature inversions. The cloud top regions precipitated low concentrations of ice into the cloud below. During the spring cases median ice number concentrations (~ 0.5 L?1) were found to be lower by about a factor of 5 than observations from the summer campaign (~ 3 L?1). Cloud layers in the summer spanned a warmer temperature regime than in the spring and enhancement of ice concentrations in these cases was found to be due to secondary ice production through the Hallett–Mossop (H–M) process. Aerosol concentrations during spring ranged from ~ 300–400 cm?3 in one case to lower values of ~ 50–100 cm?3 in the other. The concentration of aerosol with sizes Dp > 0.5 ?m was used in a primary ice nucleus (IN) prediction scheme (DeMott et al., 2010). Predicted IN values varied depending on aerosol measurement periods but were generally greater than maximum observed median values of ice crystal concentrations in the spring cases, and less than the observed ice concentrations in the summer due to the influence of secondary ice production. Comparison with recent cloud observations in the Antarctic summer (Grosvenor et al., 2012), reveals lower ice concentrations in Antarctic clouds in comparable seasons. An enhancement of ice crystal number concentrations (when compared with predicted IN numbers) was also found in Antarctic stratocumulus clouds spanning the H–M temperature zone; however, concentrations were about an order of magnitude lower than those observed in the Arctic summer cases but were similar to the peak values observed in the colder Arctic spring cases, where the H–M mechanism did not operate.

Posted on 2 April 2015 | 12:00 am


A new temperature- and humidity-dependent surface site density approach for deposition ice nucleation

A new temperature- and humidity-dependent surface site density approach for deposition ice nucleation

Atmospheric Chemistry and Physics, 15, 3703-3717, 2015

Author(s): I. Steinke, C. Hoose, O. Möhler, P. Connolly, and T. Leisner

Deposition nucleation experiments with Arizona Test Dust (ATD) as a surrogate for mineral dusts were conducted at the AIDA cloud chamber at temperatures between 220 and 250 K. The influence of the aerosol size distribution and the cooling rate on the ice nucleation efficiencies was investigated. Ice nucleation active surface site (INAS) densities were calculated to quantify the ice nucleation efficiency as a function of temperature, humidity and the aerosol surface area concentration. Additionally, a contact angle parameterization according to classical nucleation theory was fitted to the experimental data in order to relate the ice nucleation efficiencies to contact angle distributions. From this study it can be concluded that the INAS density formulation is a very useful tool to describe the temperature- and humidity-dependent ice nucleation efficiency of ATD particles.

Deposition nucleation on ATD particles can be described by a temperature- and relative-humidity-dependent INAS density function ns(T, Sice) with

ns(xtherm) = 1.88 ×105 · exp(0.2659 · xtherm) [m−2] , (1)

where the temperature- and saturation-dependent function xtherm is defined as

xtherm = −(T−273.2)+(Sice−1) ×100, (2)

with the saturation ratio with respect to ice Sice >1 and within a temperature range between 226 and 250 K. For lower temperatures, xtherm deviates from a linear behavior with temperature and relative humidity over ice.

Also, two different approaches for describing the time dependence of deposition nucleation initiated by ATD particles are proposed. Box model estimates suggest that the time-dependent contribution is only relevant for small cooling rates and low number fractions of ice-active particles.

Posted on 2 April 2015 | 12:00 am


Submicron particle mass concentrations and sources in the Amazonian wet season (AMAZE-08)

Submicron particle mass concentrations and sources in the Amazonian wet season (AMAZE-08)

Atmospheric Chemistry and Physics, 15, 3687-3701, 2015

Author(s): Q. Chen, D. K. Farmer, L. V. Rizzo, T. Pauliquevis, M. Kuwata, T. G. Karl, A. Guenther, J. D. Allan, H. Coe, M. O. Andreae, U. Pöschl, J. L. Jimenez, P. Artaxo, and S. T. Martin

Real-time mass spectra of the non-refractory species in submicron aerosol particles were recorded in a tropical rainforest in the central Amazon Basin during the wet season from February to March 2008, as a part of the Amazonian Aerosol Characterization Experiment (AMAZE-08). Organic material accounted on average for more than 80% of the non-refractory submicron particle mass concentrations during the period of measurements. There was insufficient ammonium to neutralize sulfate. In this acidic, isoprene-rich, HO2-dominant environment, positive-matrix factorization of the time series of particle mass spectra identified four statistical factors to account for the 99% of the variance in the signal intensities of the organic constituents. The first factor was identified as associated with regional and local pollution and labeled "HOA" for its hydrocarbon-like characteristics. A second factor was associated with long-range transport and labeled "OOA-1" for its oxygenated characteristics. A third factor, labeled "OOA-2," was implicated as associated with the reactive uptake of isoprene oxidation products, especially of epoxydiols to acidic haze, fog, or cloud droplets. A fourth factor, labeled "OOA-3," was consistent with an association with the fresh production of secondary organic material (SOM) by the mechanism of gas-phase oxidation of biogenic volatile organic precursors followed by gas-to-particle conversion of the oxidation products. The suffixes 1, 2, and 3 on the OOA labels signify ordinal ranking with respect to the extent of oxidation represented by the factor. The process of aqueous-phase oxidation of water-soluble products of gas-phase photochemistry might also have been associated to some extent with the OOA-2 factor. The campaign-average factor loadings had a ratio of 1.4:1 for OOA-2 : OOA-3, suggesting the comparable importance of particle-phase compared to gas-phase pathways for the production of SOM during the study period.

Posted on 2 April 2015 | 12:00 am


Simultaneous reductions in emissions of black carbon and co-emitted species will weaken the aerosol net cooling effect

Simultaneous reductions in emissions of black carbon and co-emitted species will weaken the aerosol net cooling effect

Atmospheric Chemistry and Physics, 15, 3671-3685, 2015

Author(s): Z. L. Wang, H. Zhang, and X. Y. Zhang

Black carbon (BC), a distinct type of carbonaceous material formed from the incomplete combustion of fossil and biomass based fuels under certain conditions, can interact with solar radiation and clouds through its strong light-absorption ability, thereby warming the Earth's climate system. Some studies have even suggested that global warming could be slowed down in the short term by eliminating BC emission due to its short lifetime. In this study, we estimate the influence of removing some sources of BC and other co-emitted species on the aerosol radiative effect by using an aerosol–climate atmosphere-only model BCC_AGCM2.0.1_CUACE/Aero with prescribed sea surface temperature and sea ice cover, in combination with the aerosol emissions from the Representative Concentration Pathways (RCPs) scenarios. We find that the global annual mean aerosol net cooling effect at the top of the atmosphere (TOA) will be enhanced by 0.12 W m?2 compared with recent past year 2000 levels if the emissions of only BC are reduced to the level projected for 2100 based on the RCP2.6 scenario. This will be beneficial~for the mitigation of global warming. However, both aerosol negative direct and indirect radiative effects are weakened when BC and its co-emitted species (sulfur dioxide and organic carbon) are simultaneously reduced. Relative to year 2000 levels, the global annual mean aerosol net cooling effect at the TOA will be weakened by 1.7–2.0 W m?2 if the emissions of all these aerosols are decreased to the levels projected for 2100 in different ways based on the RCP2.6, RCP4.5, and RCP8.5 scenarios. Because there are no effective ways to remove the BC exclusively without influencing the other co-emitted components, our results therefore indicate that a reduction in BC emission can lead to an unexpected warming on the Earth's climate system in the future.

Posted on 2 April 2015 | 12:00 am


OH populations and temperatures from simultaneous spectroscopic observations of 25 bands

OH populations and temperatures from simultaneous spectroscopic observations of 25 bands

Atmospheric Chemistry and Physics, 15, 3647-3669, 2015

Author(s): S. Noll, W. Kausch, S. Kimeswenger, S. Unterguggenberger, and A. M. Jones

OH rotational temperatures are widely used to derive mesopause temperatures and their variations. Since most data sets are only based on a fixed set of lines of a single band, it is important to know possible systematic uncertainties related to the choice of lines. Therefore, a comprehensive study of as many OH bands as possible is desirable. For this purpose, astronomical echelle spectrographs at large telescopes are the most suitable instruments. They offer a wide wavelength coverage, relatively high spectral resolution, and high sensitivity. Moreover, since each ground-based astronomical observation has an imprint of the Earth's atmosphere, the data archives of large astronomical facilities are a treasure for atmospheric studies. For our project, we used archival data of the medium-resolution X-shooter echelle spectrograph operated by the European Southern Observatory at Cerro Paranal in Chile. The instrument can simultaneously observe all OH bands that are accessible from ground. We reduced and analysed a set of 343 high-quality spectra taken between 2009 and 2013 to measure OH line intensities and to derive rotational and vibrational temperatures of 25 bands between 0.58 and 2.24 ?m. We studied the influence of the selected line set, OH band, upper vibrational level v′, and the molecular data on the derived level populations and temperatures. The rotational temperature results indicate differences by several degrees depending on the selection. The temperatures for bands of even and odd v′ show deviations which increase with v′. A study of the temporal variations revealed that the nocturnal variability pattern changes for v′ from 2 to 9. In particular, the spread of temperatures tends to increase during the night, and the time of the minimum temperature depends on v′. The vibrational temperatures depend on the range of v′ used for their determination, since the higher vibrational levels from 7 to 9 seem to be overpopulated compared to the lower levels. The vibrational temperature tends to increase during the night, while the intensity decreases. Our results support the assumption that the OH emission altitude depends on v′. Moreover, the emission layer appears to rise in the course of the night, which makes the OH thermalisation less efficient. The derived rotational temperatures and their change with v′ seem to be significantly affected by non-equilibrium populations.

Posted on 1 April 2015 | 12:00 am


Chemical characterization of biogenic secondary organic aerosol generated from plant emissions under baseline and stressed conditions: inter- and intra-species variability for six coniferous species

Chemical characterization of biogenic secondary organic aerosol generated from plant emissions under baseline and stressed conditions: inter- and intra-species variability for six coniferous species

Atmospheric Chemistry and Physics, 15, 3629-3646, 2015

Author(s): C. L. Faiola, M. Wen, and T. M. VanReken

The largest global source of secondary organic aerosol (SOA) in the atmosphere is derived from the oxidation of biogenic emissions. Plant stressors associated with a changing environment can alter both the quantity and composition of the compounds that are emitted. Alterations to the biogenic volatile organic compound (BVOC) profile could impact the characteristics of the SOA formed from those emissions. This study investigated the impacts of one global change stressor, increased herbivory, on the composition of SOA derived from real plant emissions. Herbivory was simulated via application of methyl jasmonate (MeJA), a proxy compound. Experiments were repeated under pre- and post-treatment conditions for six different coniferous plant types. Volatile organic compounds (VOCs) emitted from the plants were oxidized to form SOA via dark ozone-initiated chemistry. The SOA chemical composition was measured using a Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS). The aerosol mass spectra of pre-treatment biogenic SOA from all plant types tended to be similar with correlations usually greater than or equal to 0.90. The presence of a stressor produced characteristic differences in the SOA mass spectra. Specifically, the following m/z were identified as a possible biogenic stress AMS marker with the corresponding HR ion(s) shown in parentheses: m/z 31 (CH3O+), m/z 58 (C2H2O2+, C3H6O+), m/z 29 (C2H5+), m/z 57 (C3H5O+), m/z 59 (C2H3O2+, C3H7O+), m/z 71 (C3H3O2+, C4H7O+), and m/z 83 (C5H7O+). The first aerosol mass spectrum of SOA generated from the oxidation of the plant stress hormone, MeJA, is also presented. Elemental analysis results demonstrated an O : C range of baseline biogenic SOA between 0.3 and 0.47. The O : C of standard MeJA SOA was 0.52. Results presented here could be used to help identify a biogenic plant stress marker in ambient data sets collected in forest environments.

Posted on 1 April 2015 | 12:00 am


The effects of springtime mid-latitude storms on trace gas composition determined from the MACC reanalysis

The effects of springtime mid-latitude storms on trace gas composition determined from the MACC reanalysis

Atmospheric Chemistry and Physics, 15, 3605-3628, 2015

Author(s): K. E. Knowland, R. M. Doherty, and K. I. Hodges

The relationship between springtime air pollution transport of ozone (O3) and carbon monoxide (CO) and mid-latitude cyclones is explored for the first time using the Monitoring Atmospheric Composition and Climate (MACC) reanalysis for the period 2003–2012. In this study, the most intense spring storms (95th percentile) are selected for two regions, the North Pacific (NP) and the North Atlantic (NA). These storms (∼60 storms over each region) often track over the major emission sources of East Asia and eastern North America. By compositing the storms, the distributions of O3 and CO within a "typical" intense storm are examined. We compare the storm-centered composite to background composites of "average conditions" created by sampling the reanalysis data of the previous year to the storm locations. Mid-latitude storms are found to redistribute concentrations of O3 and CO horizontally and vertically throughout the storm. This is clearly shown to occur through two main mechanisms: (1) vertical lifting of CO-rich and O3-poor air isentropically, from near the surface to the mid- to upper-troposphere in the region of the warm conveyor belt; and (2) descent of O3-rich and CO-poor air isentropically in the vicinity of the dry intrusion, from the stratosphere toward the mid-troposphere. This can be seen in the composite storm's life cycle as the storm intensifies, with area-averaged O3 (CO) increasing (decreasing) between 200 and 500 hPa. The influence of the storm dynamics compared to the background environment on the composition within an area around the storm center at the time of maximum intensity is as follows. Area-averaged O3 at 300 hPa is enhanced by 50 and 36% and by 11 and 7.6% at 500 hPa for the NP and NA regions, respectively. In contrast, area-averaged CO at 300 hPa decreases by 12% for NP and 5.5% for NA, and area-averaged CO at 500 hPa decreases by 2.4% for NP while there is little change over the NA region. From the mid-troposphere, O3-rich air is clearly seen to be transported toward the surface, but the downward transport of CO-poor air is not discernible due to the high levels of CO in the lower troposphere. Area-averaged O3 is slightly higher at 1000 hPa (3.5 and 1.8% for the NP and NA regions, respectively). There is an increase of CO at 1000 hPa for the NP region (3.3%) relative to the background composite and a~slight decrease in area-averaged CO for the NA region at 1000 hPa (-2.7%).

Posted on 31 March 2015 | 12:00 am


Multi-model study of chemical and physical controls on transport of anthropogenic and biomass burning pollution to the Arctic

Multi-model study of chemical and physical controls on transport of anthropogenic and biomass burning pollution to the Arctic

Atmospheric Chemistry and Physics, 15, 3575-3603, 2015

Author(s): S. A. Monks, S. R. Arnold, L. K. Emmons, K. S. Law, S. Turquety, B. N. Duncan, J. Flemming, V. Huijnen, S. Tilmes, J. Langner, J. Mao, Y. Long, J. L. Thomas, S. D. Steenrod, J. C. Raut, C. Wilson, M. P. Chipperfield, G. S. Diskin, A. Weinheimer, H. Schlager, and G. Ancellet

Using observations from aircraft, surface stations and a satellite instrument, we comprehensively evaluate multi-model simulations of carbon monoxide (CO) and ozone (O3) in the Arctic and over lower latitude emission regions, as part of the POLARCAT Model Inter-comparison Project (POLMIP). Evaluation of 11- atmospheric models with chemistry shows that they generally underestimate CO throughout the Arctic troposphere, with the largest biases found during winter and spring. Negative CO biases are also found throughout the Northern Hemisphere, with multi-model mean gross errors (9–12%) suggesting models perform similarly over Asia, North America and Europe. A multi-model annual mean tropospheric OH (10.8 ± 0.6 × 105 molec cm?3) is found to be slightly higher than previous estimates of OH constrained by methyl chloroform, suggesting negative CO biases in models may be improved through better constraints on OH. Models that have lower Arctic OH do not always show a substantial improvement in their negative CO biases, suggesting that Arctic OH is not the dominant factor controlling the Arctic CO burden in these models. In addition to these general biases, models do not capture the magnitude of CO enhancements observed in the Arctic free troposphere in summer, suggesting model errors in the simulation of plumes that are transported from anthropogenic and biomass burning sources at lower latitudes. O3 in the Arctic is also generally underestimated, particularly at the surface and in the upper troposphere. Summer O3 comparisons over lower latitudes show several models overestimate upper tropospheric concentrations.

Simulated CO, O3 and OH all demonstrate a substantial degree of inter-model variability. Idealised CO-like tracers are used to quantitatively compare the impact of inter-model differences in transport and OH on CO in the Arctic troposphere. The tracers show that model differences in transport from Europe in winter and from Asia throughout the year are important sources of model variability at Barrow. Unlike transport, inter-model variability in OH similarly affects all regional tracers at Barrow. Comparisons of fixed-lifetime and OH-loss idealised CO-like tracers throughout the Arctic troposphere show that OH differences are a much larger source of inter-model variability than transport differences. Model OH concentrations are correlated with H2O concentrations, suggesting water vapour concentrations are linked to differences in simulated concentrations of CO and OH at high latitudes in these simulations. Despite inter-model differences in transport and OH, the relative contributions from the different source regions (North America, Europe and Asia) and different source types (anthropogenic and biomass burning) are comparable across the models. Fire emissions from the boreal regions in 2008 contribute 33, 43 and 19% to the total Arctic CO-like tracer in spring, summer and autumn, respectively, highlighting the importance of boreal fire emissions in controlling pollutant burdens in the Arctic.

Posted on 31 March 2015 | 12:00 am


Sensitivity of tropospheric loads and lifetimes of short lived pollutants to fire emissions

Sensitivity of tropospheric loads and lifetimes of short lived pollutants to fire emissions

Atmospheric Chemistry and Physics, 15, 3543-3563, 2015

Author(s): N. Daskalakis, S. Myriokefalitakis, and M. Kanakidou

The capability of global chemistry and transport models (CTMs) to simulate atmospheric composition and its spatial and temporal changes highly relies on the input data used by the models, in particular the emission inventories. Biomass burning emissions show large spatial, diurnal, seasonal and year-to-year variability. In the present study, we applied a global 3-D CTM to evaluate uncertainties in the computed atmospheric composition associated with the use of different biomass burning emissions and identify areas where observational data can help to reduce these uncertainties. We find the emission inventory choice to lead to regional differences in the calculated load of aerosols up to a factor of 4. Assumptions on the injection height of the biomass burning emissions are found to produce regionally up to 30% differences in the calculated tropospheric lifetimes of pollutants. Computed changes in lifetimes point to a strong chemical feedback mechanism between emissions from biomass burning and isoprene emissions from vegetation that are linked via NOx-driven oxidant chemistry, NOx-dependent changes in isoprene oxidation products, aerosol emissions and atmospheric transport. These interactions reduce isoprene load in the presence of biomass burning emissions by 15%, calculated for the same amount of isoprene emitted into the troposphere. Thus, isoprene load and lifetime are inversely related to the quantities of pollutants emitted by biomass burning. These interactions are shown to be able to increase the global annual secondary aerosol yield from isoprene emissions, defined as the ratio of tropospheric loads of secondary aerosol from isoprene oxidation to isoprene emissions, by up to 18%.

Posted on 31 March 2015 | 12:00 am


Rapid transport of East Asian pollution to the deep tropics

Rapid transport of East Asian pollution to the deep tropics

Atmospheric Chemistry and Physics, 15, 3565-3573, 2015

Author(s): M. J. Ashfold, J. A. Pyle, A. D. Robinson, E. Meneguz, M. S. M. Nadzir, S. M. Phang, A. A. Samah, S. Ong, H. E. Ung, L. K. Peng, S. E. Yong, and N. R. P. Harris

Anthropogenic emissions from East Asia have increased over recent decades. These increases have led to changes in atmospheric composition as far afield as North America under the prevailing westerly winds. Here we show that, during Northern Hemisphere (NH) winter, pollution originating in East Asia also directly affects atmospheric composition in the deep tropics. We present observations of marked intra-seasonal variability in the anthropogenic tracer perchloroethene (C2Cl4) collected at two locations in Borneo (117.84° E, 4.98° N and 118.00° E, 4.22° N) during the NH winter of 2008/2009. We use trajectories calculated with the Numerical Atmospheric-dispersion Modelling Environment to show that the observed enhancements in C2Cl4 mixing ratio are caused by rapid meridional transport, in the form of "cold surges", from the relatively polluted East Asian land mass. In these events air masses can move from ~35° N to Borneo in 4 days. We then present data from the Monitoring Atmospheric Composition and Climate reanalysis which suggest that air masses high in C2Cl4 may also contain levels of the pollutants carbon monoxide and ozone that are approximately double the typical "background" levels in Borneo. In addition to strengthening the meridional transport from the north, cold surges can enhance convection in Southeast Asia, and further trajectory calculations indicate that the polluted air masses can subsequently be lifted to the tropical upper troposphere. This suggests a potentially important connection between midlatitude pollution sources and the very low stratosphere.

Posted on 31 March 2015 | 12:00 am


Influence of oil and gas field operations on spatial and temporal distributions of atmospheric non-methane hydrocarbons and their effect on ozone formation in winter

Influence of oil and gas field operations on spatial and temporal distributions of atmospheric non-methane hydrocarbons and their effect on ozone formation in winter

Atmospheric Chemistry and Physics, 15, 3527-3542, 2015

Author(s): R. A. Field, J. Soltis, M. C. McCarthy, S. Murphy, and D. C. Montague

Emissions from oil and natural gas development during winter in the Upper Green River basin of Wyoming are known to drive episodic ozone (O3) production. Contrasting O3 distributions were observed in the winters of 2011 and 2012, with numerous episodes (hourly O3 ≥ 85 ppbv) in 2011 compared to none in 2012. The lack of O3 episodes in 2012 coincided with a reduction in measured ambient levels of total non-methane hydrocarbons (NMHC). Measurements of speciated NMHC, and other air quality parameters, were performed to better understand emission sources and to determine which compounds are most active in promoting O3 formation. Positive matrix factorization (PMF) analyses of the data were carried out to help achieve these goals. PMF analyses revealed three contributing factors that were identified with different emission source types: factor 1, combustion/traffic; factor 2, fugitive natural gas; and factor 3, fugitive condensate. Compositional signatures of the three contributing factors were identified through comparison with independently derived emission source profiles. Fugitive emissions of natural gas and of condensate were the two principal emission source types for NMHC. A water treatment and recycling facility was found to be a significant source of NMHC that are abundant in condensate, in particular toluene and m+p-xylene. Emissions from water treatment have an influence upon peak O3 mixing ratios at downwind measurement sites.

Posted on 31 March 2015 | 12:00 am


Step changes in persistent organic pollutants over the Arctic and their implications

Step changes in persistent organic pollutants over the Arctic and their implications

Atmospheric Chemistry and Physics, 15, 3479-3495, 2015

Author(s): Y. Zhao, T. Huang, L. Wang, H. Gao, and J. Ma

While some persistent organic pollutants (POPs) have been declining globally due to their worldwide ban since the 1980s, the declining trends of many of these toxic chemicals become less significant and in some cases their ambient air concentrations, e.g., polychlorinated biphenyls (PCBs), showed observable increase during the 2000s, disagreeing with their declining global emissions and environmental degradation. As part of the efforts to assess the influences of environmental factors on the long-term trend of POPs in the Arctic, step change points in the time series of ambient POP atmospheric concentrations collected from four arctic monitoring sites were examined using various statistical techniques. Results showed that the step change points of these POP data varied in different years and at different sites. Most step change points were found in 2001–2002 and 2007–2008. In particular, the step change points of many PCBs for 2007–2008 were coincident with the lowest arctic sea ice concentration occurring during the 2000s. The perturbations of air concentration and water–air exchange fluxes of several selected POPs averaged over the Arctic, simulated by a POP mass balance perturbation model, switched from negative to positive during the early 2000s, indicating a tendency for reversal of POPs from deposition to volatilization which coincides with a positive to negative reversal of arctic sea ice extent anomalies from 2001. Perturbed ice–air exchange flux of PCB 28 and 153 showed an increasing trend and a negative to positive reversal in 2007, the year with the lowest arctic sea ice concentration. On the other hand, perturbed ice–air exchange flux of ?-hexachlorocyclohexane decreased over the period of 1995 to 2012, likely owing to its lower Henry's law constant which indicates its relatively lower tendency for volatilization from ice to air.

Posted on 31 March 2015 | 12:00 am


Aerosol processing and CCN formation of an intense Saharan dust plume during the EUCAARI 2008 campaign

Aerosol processing and CCN formation of an intense Saharan dust plume during the EUCAARI 2008 campaign

Atmospheric Chemistry and Physics, 15, 3497-3516, 2015

Author(s): N. Bègue, P. Tulet, J. Pelon, B. Aouizerats, A. Berger, and A. Schwarzenboeck

Atmospheric processing and CCN formation of Saharan dust is illustrated through the analysis of a case of dust transport over northern Europe. This spread of dust is investigated by combining satellite, airborne and ground-based observations and the non-hydrostatic meso-scale model Meso-NH. The altitude of the dust plume during its transport to northwestern Europe was assessed using the CALIPSO observations and our model results. The major dust plume was transported toward Mediterranean and European regions between 2 and 5 km above sea level (a.s.l.). This is confirmed by an average particle depolarization ratio equal to 30%. Due to transport, this layer split into two layers over northern Europe, and we analyzed in this paper possible mixing of the European pollution aerosol with dust particles in the lower layer. The simulations have shown that the lower dust layer has interacted with the anthropogenic aerosol mainly over Belgium and the Netherlands. The analyses of numerical simulation results show that mineral dust particles accumulated soluble material through internal mixing over the Netherlands. The value of the CCN0.2 / CN ratio obtained over the Netherlands (~ 70%) is much greater than those observed over the Saharan region. In addition over the Netherlands, the CCN measurement reached 14 000 particles cm?3 at 0.63% supersaturation level on 30 May. Our model results reveal that more than 70% of the CCN concentration observed on 30 May can be explained by the presence of Saharan aged dust. The study reveals that heterogeneous reactions with inorganic salts converted this Saharan mineral dust into compounds that were sufficiently soluble to impact hygroscopic growth and cloud droplet activation over the Netherlands.

Posted on 31 March 2015 | 12:00 am


The impact of temperature vertical structure on trajectory modeling of stratospheric water vapor

The impact of temperature vertical structure on trajectory modeling of stratospheric water vapor

Atmospheric Chemistry and Physics, 15, 3517-3526, 2015

Author(s): T. Wang, A. E. Dessler, M. R. Schoeberl, W. J. Randel, and J.-E. Kim

Lagrangian trajectories driven by reanalysis meteorological fields are frequently used to study water vapor (H2O) in the stratosphere, in which the tropical cold-point temperatures regulate the amount of H2O entering the stratosphere. Therefore, the accuracy of temperatures in the tropical tropopause layer (TTL) is of great importance for understanding stratospheric H2O abundances. Currently, most reanalyses, such as the NASA MERRA (Modern Era Retrospective – analysis for Research and Applications), only provide temperatures with ~ 1.2 km vertical resolution in the TTL, which has been argued to miss finer vertical structure in the tropopause and therefore introduce uncertainties in our understanding of stratospheric H2O. In this paper, we quantify this uncertainty by comparing the Lagrangian trajectory prediction of H2O using MERRA temperatures on standard model levels (traj.MER-T) to those using GPS temperatures at finer vertical resolution (traj.GPS-T), and those using adjusted MERRA temperatures with finer vertical structures induced by waves (traj.MER-Twave). It turns out that by using temperatures with finer vertical structure in the tropopause, the trajectory model more realistically simulates the dehydration of air entering the stratosphere. But the effect on H2O abundances is relatively minor: compared with traj.MER-T, traj.GPS-T tends to dry air by ~ 0.1 ppmv, while traj.MER-Twave tends to dry air by 0.2–0.3 ppmv. Despite these differences in absolute values of predicted H2O and vertical dehydration patterns, there is virtually no difference in the interannual variability in different runs. Overall, we find that a tropopause temperature with finer vertical structure has limited impact on predicted stratospheric H2O.

Posted on 31 March 2015 | 12:00 am


Estimated desert-dust ice nuclei profiles from polarization lidar: methodology and case studies

Estimated desert-dust ice nuclei profiles from polarization lidar: methodology and case studies

Atmospheric Chemistry and Physics, 15, 3463-3477, 2015

Author(s): R. E. Mamouri and A. Ansmann

A lidar method is presented that permits the estimation of height profiles of ice nuclei concentrations (INC) in desert dust layers. The polarization lidar technique is applied to separate dust and non-dust backscatter and extinction coefficients. The desert dust extinction coefficients σd are then converted to aerosol particle number concentrations APC280 which consider particles with radius > 280 nm only. By using profiles of APC280 and ambient temperature T along the laser beam, the profile of INC can be estimated within a factor of 3 by means of APC-T-INC parameterizations from the literature. The observed close relationship between σd at 500 nm and APC280 is of key importance for a successful INC retrieval. We studied this link by means of AERONET (Aerosol Robotic Network) sun/sky photometer observations at Morocco, Cabo Verde, Barbados, and Cyprus during desert dust outbreaks. The new INC retrieval method is applied to lidar observations of dust layers with the spaceborne lidar CALIOP (Cloud Aerosol Lidar with Orthogonal Polarization) during two overpasses over the EARLINET (European Aerosol Research Lidar Network) lidar site of the Cyprus University of Technology (CUT), Limassol (34.7° N, 33° E), Cyprus. The good agreement between the CALIOP and CUT lidar retrievals of σd, APC280, and INC profiles corroborates the potential of CALIOP to provide 3-D global desert dust APC280 and INC data sets.

Posted on 30 March 2015 | 12:00 am


Long-term particulate matter modeling for health effect studies in California – Part 1: Model performance on temporal and spatial variations

Long-term particulate matter modeling for health effect studies in California – Part 1: Model performance on temporal and spatial variations

Atmospheric Chemistry and Physics, 15, 3445-3461, 2015

Author(s): J. Hu, H. Zhang, Q. Ying, S.-H. Chen, F. Vandenberghe, and M. J. Kleeman

For the first time, a ~ decadal (9 years from 2000 to 2008) air quality model simulation with 4 km horizontal resolution over populated regions and daily time resolution has been conducted for California to provide air quality data for health effect studies. Model predictions are compared to measurements to evaluate the accuracy of the simulation with an emphasis on spatial and temporal variations that could be used in epidemiology studies. Better model performance is found at longer averaging times, suggesting that model results with averaging times ≥ 1 month should be the first to be considered in epidemiological studies. The UCD/CIT model predicts spatial and temporal variations in the concentrations of O3, PM2.5, elemental carbon (EC), organic carbon (OC), nitrate, and ammonium that meet standard modeling performance criteria when compared to monthly-averaged measurements. Predicted sulfate concentrations do not meet target performance metrics due to missing sulfur sources in the emissions. Predicted seasonal and annual variations of PM2.5, EC, OC, nitrate, and ammonium have mean fractional biases that meet the model performance criteria in 95, 100, 71, 73, and 92% of the simulated months, respectively. The base data set provides an improvement for predicted population exposure to PM concentrations in California compared to exposures estimated by central site monitors operated 1 day out of every 3 days at a few urban locations.

Uncertainties in the model predictions arise from several issues. Incomplete understanding of secondary organic aerosol formation mechanisms leads to OC bias in the model results in summertime but does not affect OC predictions in winter when concentrations are typically highest. The CO and NO (species dominated by mobile emissions) results reveal temporal and spatial uncertainties associated with the mobile emissions generated by the EMFAC 2007 model. The WRF model tends to overpredict wind speed during stagnation events, leading to underpredictions of high PM concentrations, usually in winter months. The WRF model also generally underpredicts relative humidity, resulting in less particulate nitrate formation, especially during winter months. These limitations must be recognized when using data in health studies. All model results included in the current manuscript can be downloaded free of charge at http://faculty.engineering.ucdavis.edu/kleeman/ .

Posted on 30 March 2015 | 12:00 am


Total sulfate vs. sulfuric acid monomer concenterations in nucleation studies

Total sulfate vs. sulfuric acid monomer concenterations in nucleation studies

Atmospheric Chemistry and Physics, 15, 3429-3443, 2015

Author(s): K. Neitola, D. Brus, U. Makkonen, M. Sipilä, R. L. Mauldin III, N. Sarnela, T. Jokinen, H. Lihavainen, and M. Kulmala

Sulfuric acid is known to be a key component for atmospheric nucleation. Precise determination of sulfuric-acid concentration is a crucial factor for prediction of nucleation rates and subsequent growth. In our study, we have noticed a substantial discrepancy between sulfuric-acid monomer concentrations and total-sulfate concentrations measured from the same source of sulfuric-acid vapor. The discrepancy of about 1–2 orders of magnitude was found with similar particle-formation rates. To investigate this discrepancy, and its effect on nucleation, a method of thermally controlled saturator filled with pure sulfuric acid (97% wt.) for production of sulfuric-acid vapor is applied and rigorously tested. The saturator provided an independent vapor-production method, compared to our previous method of the furnace (Brus et al., 2010, 2011), to find out if the discrepancy is caused by the production method itself. The saturator was used in a H2SO4–H2O nucleation experiment, using a laminar flow tube to check reproducibility of the nucleation results with the saturator method, compared to the furnace. Two independent methods of mass spectrometry and online ion chromatography were used for detecting sulfuric-acid or sulfate concentrations. Measured sulfuric-acid or total-sulfate concentrations are compared to theoretical predictions calculated using vapor pressure and a mixing law. The calculated prediction of sulfuric-acid concentrations agrees very well with the measured values when total sulfate is considered. Sulfuric-acid monomer concentration was found to be about 2 orders of magnitude lower than theoretical predictions, but with a temperature dependency similar to the predictions and the results obtained with the ion-chromatograph method. Formation rates are reproducible when compared to our previous results with both sulfuric-acid or total-sulfate detection and sulfuric-acid production methods separately, removing any doubts that the vapor-production method would cause the discrepancy. Possible reasons for the discrepancy are discussed and some suggestions include that the missing sulfuric acid is in clusters, formed with contaminants found in most laboratory experiments. One-to-two-order-of-magnitude higher sulfuric-acid concentrations (measured as total sulfate in this study) would contribute to a higher fraction of particle growth rate than assumed from the measurements by mass spectrometers (i.e. sulfuric-acid monomer). However, the observed growth rates by sulfate-containing vapor in this study does not directly imply a similar situation in the field, where sources of sulfate are much more diverse.

Posted on 28 March 2015 | 12:00 am


Major contribution of neutral clusters to new particle formation at the interface between the boundary layer and the free troposphere

Major contribution of neutral clusters to new particle formation at the interface between the boundary layer and the free troposphere

Atmospheric Chemistry and Physics, 15, 3413-3428, 2015

Author(s): C. Rose, K. Sellegri, E. Asmi, M. Hervo, E. Freney, A. Colomb, H. Junninen, J. Duplissy, M. Sipilä, J. Kontkanen, K. Lehtipalo, and M. Kulmala

The formation of new aerosol particles in the atmosphere is a key process influencing the aerosol number concentration as well as the climate, in particular at high altitude, where the newly formed particles directly influence cloud formation. However, free tropospheric new particle formation (NPF) is poorly documented due to logistic limitations and complex atmospheric dynamics around high-altitude stations that make the observation of this day-time process challenging. Recent improvements in measurement techniques make now possible the detection of neutral clusters down to ~ 1 nm sizes, which opens new horizons in our understanding of the nucleation process. Indeed, only the charged fraction of clusters has been reported in the upper troposphere up to now. Here we report day-time concentrations of charged and neutral clusters (1 to 2.5 nm mobility diameter) recorded at the interface between the boundary layer (BL) and the FT as well as in the FT at the altitude site of Puy de Dôme (1465 m a.s.l.), central France, between 10 and 29 February 2012. Our findings demonstrate that in the FT, and especially at the interface between the BL and the FT, the formation of 1.5 nm neutral clusters significantly exceeds the one of ionic clusters during NPF events, clearly indicating that they dominate in the nucleation process. We also observe that the total cluster concentration significantly increases during NPF events compared to the other days, which was not clearly observed for the charged cluster population in the past. During the studied period, the nucleation process does not seem to be sulfuric acid-limited and could be promoted by the transport of pollutants to the upper troposphere, coupled with low temperatures.

Posted on 27 March 2015 | 12:00 am


Using the chemical equilibrium partitioning space to explore factors influencing the phase distribution of compounds involved in secondary organic aerosol formation

Using the chemical equilibrium partitioning space to explore factors influencing the phase distribution of compounds involved in secondary organic aerosol formation

Atmospheric Chemistry and Physics, 15, 3395-3412, 2015

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

Many atmospheric and chemical variables influence the partitioning equilibrium between gas phase and condensed phases of compounds implicated in the formation of secondary organic aerosol (SOA). The large number of factors and their interaction makes it often difficult to assess their relative importance and concerted impact. Here we introduce a two-dimensional space which maps regions of dominant atmospheric phase distribution within a coordinate system defined by equilibrium partition coefficients between the gas phase, an aqueous phase and a water-insoluble organic matter (WIOM) phase. Placing compounds formed from the oxidation of n-alkanes, terpenes and mono-aromatic hydrocarbons on the maps based on their predicted partitioning properties allows for a simple graphical assessment of their equilibrium phase distribution behaviour. Specifically, it allows for the simultaneous visualisation and quantitative comparison of the impact on phase distribution of changes in atmospheric parameters (such as temperature, salinity, WIOM-phase polarity, organic aerosol load, and liquid water content) and chemical properties (such as oxidation state, molecular size, functionalisation, and dimerisation). The graphical analysis reveals that the addition of hydroxyl, carbonyl and carboxyl groups increases the affinity of aliphatic, alicyclic and aromatic hydrocarbons for the aqueous phase more rapidly than their affinity for WIOM, suggesting that the aqueous phase may often be relevant even for substances that are considerably larger than the C2 and C3 compounds that are typically believed to be associated with aqueous SOA. In particular, the maps identify some compounds that contribute to SOA formation if partitioning to both WIOM and aqueous phase is considered but would remain in the gas phase if either condensed phase were neglected. For example, many semi-volatile ?-pinene oxidation products will contribute to aqueous SOA under the conditions of high liquid water content encountered in clouds but would remain vapours in wet aerosol. It is conceivable to develop parameterisations of "partitioning basis sets" that group compounds with comparable partitioning properties, which – when combined with data on the abundance of those groups of compounds – could serve in the simulation of SOA formation.

Posted on 27 March 2015 | 12:00 am


Hygroscopic properties of NaCl and NaNO3 mixture particles as reacted inorganic sea-salt aerosol surrogates

Hygroscopic properties of NaCl and NaNO3 mixture particles as reacted inorganic sea-salt aerosol surrogates

Atmospheric Chemistry and Physics, 15, 3379-3393, 2015

Author(s): D. Gupta, H. Kim, G. Park, X. Li, H.-J. Eom, and C.-U. Ro

NaCl in fresh sea-salt aerosol (SSA) particles can partially or fully react with atmospheric NOx/HNO3, so internally mixed NaCl and NaNO3 aerosol particles can co-exist over a wide range of mixing ratios. Laboratory-generated, micrometer-sized NaCl and NaNO3 mixture particles at 10 mixing ratios (mole fractions of NaCl (XNaCl) = 0.1 to 0.9) were examined systematically to observe their hygroscopic behavior, derive experimental phase diagrams for deliquescence and efflorescence, and understand the efflorescence mechanism. During the humidifying process, aerosol particles with the eutonic composition (XNaCl = 0.38) showed only one phase transition at their mutual deliquescence relative humidity (MDRH) of 67.9 (±0.5)% On the other hand, particles with other mixing ratios showed two distinct deliquescence transitions; i.e., the eutonic component dissolved at MDRH, and the remainder in the solid phase dissolved completely at their DRHs depending on the mixing ratios, resulting in a phase diagram composed of four different phases, as predicted thermodynamically. During the dehydration process, NaCl-rich particles (XNaCl > 0.38) showed a two stage efflorescence transition: the first stage was purely driven by the homogeneous nucleation of NaCl and the second stage at the mutual efflorescence RH (MERH) of the eutonic components, with values in the range of 30.0–35.5%. Interestingly, aerosol particles with the eutonic composition (XNaCl = 0.38) also showed two-stage efflorescence, with NaCl crystallizing first followed by heterogeneous nucleation of the remaining NaNO3 on the NaCl seeds. NaNO3-rich particles (XNaCl ≤ 0.3) underwent single-stage efflorescence transitions at ERHs progressively lower than the MERH because of the homogeneous nucleation of NaCl and the almost simultaneous heterogeneous nucleation of NaNO3 on the NaCl seeds. SEM/EDX elemental mapping indicated that the effloresced NaCl–NaNO3 particles at all mixing ratios were composed of a homogeneously crystallized NaCl moiety in the center, surrounded either by the eutonic component (for XNaCl > 0.38) or NaNO3 (for XNaCl ≤ 0.38). During the humidifying or dehydration process, the amount of eutonic composed part drives particle/droplet growth or shrinkage at the MDRH or MERH (second ERH), respectively, and the amount of pure salts (NaCl or NaNO3 in NaCl- or NaNO3-rich particles, respectively) drives the second DRHs or first ERHs, respectively. Therefore, their behavior can be a precursor to the optical properties and direct radiative forcing for these atmospherically relevant mixture particles representing the coarse, reacted inorganic SSAs. In addition, the NaCl–NaNO3 mixture aerosol particles can maintain an aqueous phase over a wider RH range than pure NaCl particles as SSA surrogate, making their heterogeneous chemistry more probable.

Posted on 26 March 2015 | 12:00 am


Diel and seasonal changes of biogenic volatile organic compounds within and above an Amazonian rainforest

Diel and seasonal changes of biogenic volatile organic compounds within and above an Amazonian rainforest

Atmospheric Chemistry and Physics, 15, 3359-3378, 2015

Author(s): A. M. Yáñez-Serrano, A. C. Nölscher, J. Williams, S. Wolff, E. Alves, G. A. Martins, E. Bourtsoukidis, J. Brito, K. Jardine, P. Artaxo, and J. Kesselmeier

The Amazonian rainforest is a large tropical ecosystem, which is one of the last pristine continental terrains. This ecosystem is ideally located for the study of diel and seasonal behaviour of biogenic volatile organic compounds (BVOCs) in the absence of local human interference. In this study, we report the first atmospheric BVOC measurements at the Amazonian Tall Tower Observatory (ATTO) site, located in central Amazonia. A quadrupole proton-transfer-reaction mass spectrometer (PTR-MS), with seven ambient air inlets, positioned from near ground to about 80 m (0.05, 0.5, 4, 24, 38, 53 and 79 m above the forest floor), was deployed for BVOC monitoring. We report diel and seasonal (February–March 2013 as wet season and September 2013 as dry season) ambient mixing ratios for isoprene, monoterpenes, isoprene oxidation products, acetaldehyde, acetone, methyl ethyl ketone (MEK), methanol and acetonitrile. Clear diel and seasonal patterns were observed for all compounds. In general, lower mixing ratios were observed during night, while maximum mixing ratios were observed during the wet season (February–March 2013), with the peak in solar irradiation at 12:00 LT (local time) and during the dry season (September 2013) with the peak in temperature at 16:00 LT. Isoprene and monoterpene mixing ratios were the highest within the canopy with a median of 7.6 and 1 ppb, respectively (interquartile range (IQR) of 6.1 and 0.38 ppb) during the dry season (at 24 m, from 12:00 to 15:00 LT). The increased contribution of oxygenated volatile organic compounds (OVOCs) above the canopy indicated a transition from dominating forest emissions during the wet season (when mixing ratios were higher than within the canopy), to a blend of biogenic emission, photochemical production and advection during the dry season when mixing ratios were higher above the canopy. Our observations suggest strong seasonal interactions between environmental (insolation, temperature) and biological (phenology) drivers of leaf BVOC emissions and atmospheric chemistry. Considerable differences in the magnitude of BVOC mixing ratios, as compared to other reports of Amazonian BVOC, demonstrate the need for long-term observations at different sites and more standardized measurement procedures, in order to better characterize the natural exchange of BVOCs between the Amazonian rainforest and the atmosphere.

Posted on 25 March 2015 | 12:00 am


Relating hygroscopicity and optical properties to chemical composition and structure of secondary organic aerosol particles generated from the ozonolysis of ?-pinene

Relating hygroscopicity and optical properties to chemical composition and structure of secondary organic aerosol particles generated from the ozonolysis of ?-pinene

Atmospheric Chemistry and Physics, 15, 3339-3358, 2015

Author(s): C. Denjean, P. Formenti, B. Picquet-Varrault, E. Pangui, P. Zapf, Y. Katrib, C. Giorio, A. Tapparo, A. Monod, B. Temime-Roussel, P. Decorse, C. Mangeney, and J. F. Doussin

Secondary organic aerosol (SOA) were generated from the ozonolysis of ?-pinene in the CESAM (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber) simulation chamber. The SOA formation and aging were studied by following their optical, hygroscopic and chemical properties. The optical properties were investigated by determining the particle complex refractive index (CRI). The hygroscopicity was quantified by measuring the effect of relative humidity (RH) on the particle size (size growth factor, GF) and on the scattering coefficient (scattering growth factor, f(RH)). The oxygen to carbon atomic ratios (O : C) of the particle surface and bulk were used as a sensitive parameter to correlate the changes in hygroscopic and optical properties of the SOA composition during their formation and aging in CESAM.

The real CRI at 525 nm wavelength decreased from 1.43–1.60 (±0.02) to 1.32–1.38 (±0.02) during the SOA formation. The decrease in the real CRI correlated to the O : C decrease from 0.68 (±0.20) to 0.55 (±0.16). In contrast, the GF remained roughly constant over the reaction time, with values of 1.02–1.07 (±0.02) at 90% (±4.2%) RH. Simultaneous measurements of O : C of the particle surface revealed that the SOA was not composed of a homogeneous mixture, but contained less oxidised species at the surface which may limit water absorption. In addition, an apparent change in both mobility diameter and scattering coefficient with increasing RH from 0 to 30% was observed for SOA after 14 h of reaction. We postulate that this change could be due to a change in the viscosity of the SOA from a predominantly glassy state to a predominantly liquid state.

Posted on 25 March 2015 | 12:00 am





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