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The sensitivity of secondary organic aerosol component partitioning to the predictions of component properties – Part 1: A systematic evaluation of some available estimation techniques

A large number of calculations of the absorptive partitioning of organic compounds have been made using a number of methods to predict the component vapour pressures, p0, and activity coefficients, γi, required in the calculations. The sensitivities of the predictions in terms of the condensed component masses, volatility, O:C ratio, molar mass and functionality distributions to the choice of p0 and γi models and to the number of components to represent the organic mixture have been systematically compared. The condensed component mass was found to be highly sensitive to the vapour pressure model, and less sensitive to both the activity coefficient model and the number of components used to represent the mixture although the sensitivity to the change in property estimation method increased substantially with increased simplification in the treatment of the organic mixture. This was a general finding and was also clearly evident in terms of the predicted component functionality, O:C ratio, molar mass and volatility distributions of the condensed organic components. Within the limitations of the study, this clearly demonstrates the requirement for more accurate representation of the p0 and γi of the semi-volatile organic proxy components used in simplified models as the degree of simplification increases. This presents an interesting paradox, since such reduction in complexity necessarily leads to divergence from the complex behaviour of real multicomponent atmospheric aerosol.
Emission and dry deposition of accumulation mode particles in the Amazon Basin

Size-resolved vertical aerosol number fluxes of particles in the diameter range 0.25–2.5 μm were measured with the eddy covariance method from a 53 m high tower over the Amazon rain forest, 60 km NNW of Manaus, Brazil. This study focuses on data measured during the relatively clean wet season, but a shorter measurement period from the more polluted dry season is used as a comparison. Size-resolved net particle fluxes of the five lowest size bins, representing 0.25–0.45 μm in diameter, were in general dominated by deposition in more or less all wind sectors in the wet season. This is an indication that the source of primary biogenic aerosol particles may be small in this particle size range. Transfer velocities within this particle size range were observed to increase linearly with increasing friction velocity and increasing particle diameter. In the diameter range 0.5–2.5 μm, vertical particle fluxes were highly dependent on wind direction. In wind sectors where anthropogenic influence was low, net upward fluxes were observed. However, in wind sectors associated with higher anthropogenic influence, deposition fluxes dominated. The net upward fluxes were interpreted as a result of primary biogenic aerosol emission, but deposition of anthropogenic particles seems to have masked this emission in wind sectors with higher anthropogenic influence. The net emission fluxes were at maximum in the afternoon when the mixed layer is well developed, and were best correlated with horizontal wind speed according to the equation log10 F=0.48 · U+2.21 where F is the net emission number flux of 0.5–2.5 μm particles [m−2 s−1] and U is the horizontal wind speed [ms−1] at the top of the tower.
Evidence of the impact of deep convection on reactive Volatile Organic Compounds in the upper tropical troposphere during the AMMA experiment in West Africa

A large dataset of reactive trace gases was collected for the first time over West Africa during the African Monsoon Multidisciplinary Analysis (AMMA) field experiment in August 2006. Volatile Organic Compounds (VOC from C5–C9) were measured onboard the two French aircrafts the ATR-42 and the Falcon-20 by a new instrument AMOVOC (Airborne Measurement Of Volatile Organic Compounds). The goal of this study is (i) to characterize VOC distribution in the tropical region of West Africa (ii) to determine the impact of deep convection on VOC distribution and chemistry in the tropical upper troposphere (UT) and (iii) to characterize its spatial and temporal extensions. Experimental strategy consisted in sampling at altitudes between 0 and 12 km downwind of Mesoscale Convective Systems (MCS) and at cloud base. Biogenic and anthropogenic VOC distribution in West Africa is clearly affected by North to South emission gradient. Isoprene, the most abundant VOC, is at maximum level over the forest (1.26 ppb) while benzene reaches its maximum over the urban areas (0.11 ppb). First, a multiple physical and chemical tracers approach using CO, O3 and relative humidity was implemented to distinguish between convective and non-convective air masses. Then, additional tools based on VOC observations (tracer ratios, proxy of emissions and photochemical clocks) were adapted to characterize deep convection on a chemical, spatial and temporal basis. VOC vertical profiles show a "C-shaped" trend indicating that VOC-rich air masses are transported from the surface to the UT by deep convective systems. VOC mixing ratios in convective outflow are up to two times higher than background levels even for reactive and short-lived VOC (e.g. isoprene up to 0.19 ppb at 12 km-altitude) and are dependent on surface emission type. As a consequence, UT air mass reactivity increases from 0.52 s−1 in non-convective conditions to 0.95 s−1 in convective conditions. Fractions of boundary layer air contained in convective outflow are estimated to be 40 ± 15%. Vertical transport timescale is calculated to be 25 ± 10 min between 0 to 12 km altitude. These results characterize deep convection occurring over West Africa and provide relevant information for tropical convection parameterization in regional/global models.
Variability of the nighttime OH layer and mesospheric ozone at high latitudes during northern winter: influence of meteorology

Analyses of OH zonal means, recorded at boreal high latitudes by the Aura Microwave Limb Sounder (MLS) in winters of 2005–2009, have shown medium- (weeks) and short- (days) term variability of the nighttime OH layer. Because of the exceptional descent of air from the mesosphere-lower thermosphere (MLT) region, medium-term variability occurred during February 2006 and February/March 2009. The layer normally situated at about 82 km descended by about 5–7 km, and its density increased to more than twice January values. In these periods and location the abundance of the lowered OH layer is comparable to the OH values induced by Solar Energetic Particle (SEP) forcing (e.g., SEP events of January 2005) at the same altitudes. In both years, the descent of the OH layer was coupled with increased mesospheric temperatures, elevated carbon monoxide and an almost complete disappearance of ozone at the altitude of the descended layer (which was not observed in other years). Moreover, under these exceptional atmospheric conditions, the third ozone peak, normally at about 72 km, is shown to descend about 5 km to lower altitude and increase in magnitude, with maximum values recorded during February 2009. Short-term variability occurred during Sudden Stratospheric Warming (SSW) events, in particular in January 2006, February 2008 and January 2009, when dynamics led to a smaller abundance of the OH layer at its typical altitude. During these periods, there was an upward displacement of the OH layer coupled to changes in ozone and carbon monoxide. These perturbations were the strongest during the SSW of January 2009; coincident upper mesospheric temperatures were the lowest recorded over the late winters of 2005–2009. Finally, the series of SSW events that occurred in late January/February 2008 induced noticeable short-term variability in ozone at altitudes of both the ozone minimum and the third ozone peak. These phenomena, confined inside the polar vortex, are an additional tool that can be used to investigate mesospheric vortex dynamics.
Dynamics of the Antarctic and Arctic mesosphere and lower thermosphere – Part 1: Mean winds

Zonal and meridional winds have been measured in the upper mesosphere and lower thermosphere at polar latitudes using two ground-based meteor radars. One radar is located at Rothera (68° S, 68° W) in the Antarctic and has been operational since February 2005. The second radar is located at Esrange (68° N, 21° E) in the Arctic and has been operational since October 1999. Both radars have produced relatively continuous measurements. Here we consider measurements made up to the end of 2009. Both radars are of similar design and at conjugate geographical latitudes, making the results directly comparable and thus allowing investigation of the differences in the mean winds of the Antarctic and Arctic regions. The data from each radar have been used to construct climatologies of monthly-mean zonal and meridional winds at heights between 80 and 100 km. Both Antarctic and Arctic data sets reveal seasonally varying zonal and meridional winds in which the broad pattern repeats from year to year. In particular, the zonal winds display a strong shear in summer associated with the upper part of the westward summertime zonal jet. The winds generally reverse to eastward flow at heights of ~90 km. The zonal winds are eastward throughout the rest of the year. The meridional winds are generally equatorward over both sites, although brief episodes of poleward flow are often evident near the equinoxes and during winter. The strongest equatorward flows occur at heights of ~90 km during summer. There are significant differences between the mean winds observed in the Antarctic and Arctic. In particular, the westward winds in summer are stronger and occur earlier in the season in the Antarctic compared with the Arctic. The eastward winds evident above the summertime zonal wind reversal are significantly stronger in the Arctic. The summertime equatorward flow in the Antarctic is slightly weaker, but occurs over a greater depth than is the case in the Arctic. Comparisons of these observations with those of the URAP and HWM-07 empirical models reveal a number of significant differences. In particular, the zonal winds observed in the Antarctic during wintertime are significantly weaker than those of URAP. However, the URAP zonal winds are a good match to the observations of the Arctic. Significant differences are evident between the observations and HWM-07. In particular, the strong wintertime zonal winds of the Arctic in HWM-07 are not evident in the observations and the summertime zonal winds in HWM-07 are systematically stronger than observed. The agreement with meridional winds is generally poor. There is a significant amount of inter-annual variability in the observed zonal and meridional winds. Particularly high variability is observed in the Arctic zonal winds in spring and is probably associated with stratospheric warmings.
Review and parameterisation of bi-directional ammonia exchange between vegetation and the atmosphere

Current deposition schemes used in atmospheric chemical transport models do not generally account for bi-directional exchange of ammonia (NH3). Bi-directional exchange schemes, which have so far been applied at the plot scale, can be included in transport models, but need to be parameterised with appropriate values of the ground layer compensation point (χg), stomatal compensation point (χs) and cuticular resistance (Rw). We review existing measurements of χg, χs as well as Rw and compile a comprehensive dataset from which we then propose generalised parameterisations. χs is related to Γs, the non-dimensional ratio of [NH4+]apo and [H+]apo in the apoplast, through the temperature dependence of the combined Henry and dissociation equilibrium. The meta-analysis suggests that the nitrogen (N) input is the main driver of the apoplastic and bulk leaf concentrations of ammonium (NH4 apo<sup+, NH4 bulk<sup+). For managed ecosystems, the main source of N is fertilisation which is reflected in a peak value of χs a few days following application, but also alters seasonal values of NH4 apo<sup+ and NH4 bulk<sup+. We propose a parameterisation for χs which includes peak values as a function of amount and type of fertiliser application which gradually decreases to a background value. The background χs is based on total N input to the ecosystem as a yearly fertiliser application and N deposition (Ndep). For non-managed ecosystems, χs is parameterised based solely on the link with Ndep. For Rw we propose a general parameterisation as a function of atmospheric relative humidity (RH), incorporating a minimum value (Rw(min)), which depends on the ratio of atmospheric acid concentrations (SO2, HNO3 and HCl) to NH3 concentrations. The parameterisations are based mainly on datasets from temperate locations in northern Europe making them most suitable for up-scaling in these regions (EMEP model for example). In principle, the parameterisations should be applicable to other climates, though there is a need for more underpinning data, with the uncertainties being especially large for tropical and subtropical conditions.
Heterogeneous reactions of carbonyl sulfide on mineral oxides: mechanism and kinetics study

The heterogeneous reactions of carbonyl sulfide (OCS) on the typical mineral oxides in the mineral dust particles were investigated using a Knudsen cell flow reactor and a diffuse reflectance UV-vis spectroscopy. The reaction pathway for OCS on mineral dust was identified based on the gaseous products and surface species. The hydrolysis of OCS and succeeding oxidation of intermediate products readily took place on α-Al2O3, MgO, and CaO. Reversible and irreversible adsorption of OCS were observed on α-Fe2O3 and ZnO, respectively, whereas no apparent uptake of OCS by SiO2 and TiO2 was observed. The reactivity of OCS on these oxides depends on both the basicity of oxides and the decomposition reactivity of oxides for H2S. Based on the individual uptake coefficients and chemical composition of authentic mineral dust, the uptake coefficient (γBET) of mineral dust was estimated to be in the range of 3.84×10−7–2.86×10−8. The global flux of OCS due to heterogeneous reactions and adsorption on mineral dust was estimated at 0.13–0.29 Tg yr−1, which is comparable to the annual flux of OCS for its reaction with ·OH.
Optical-chemical-microphysical relationships and closure studies for mixed carbonaceous aerosols observed at Jeju Island; 3-laser photoacoustic spectrometer, particle sizing, and filter analysis

Transport of aerosols in pollution plumes from the mainland Asian continent was observed in situ at Jeju, South Korea during the Cheju Asian Brown Cloud Plume-Asian Monsoon Experiment (CAPMEX) field campaign throughout August and September 2008 using a 3-laser photoacoustic spectrometer (PASS-3), chemical filter analysis, and size distributions. The PASS-3 directly measures the effects of morphology (e.g. coatings) on light absorption that traditional filter-based instruments are unable to address. Transport of mixed sulfate, carbonaceous, and nitrate aerosols from various Asian pollution plumes to Jeju accounted for 74% of the deployment days, showing large variations in their measured chemical and optical properties. Analysis of eight distinct episodes, spanning wide ranges of chemical composition, optical properties, and source regions, reveals that episodes with higher organic carbon (OC)/sulfate (SO42−) and nitrate (NO3−)/SO42− composition ratios exhibit lower single scatter albedo at shorter wavelengths (ω405). We infer complex refractive indices (n–ik) as a function of wavelength for the high, intermediate, and low OC/SO42− pollution episodes by using the observed particle size distributions and the measured optical properties. The smallest mean particle diameter corresponds to the high OC/SO42− aerosol episode. The imaginary part of the refractive index (k) is greater for the high OC/SO42− episode at all wavelengths. A distinct, sharp increase in k at short wavelength implies enhanced light absorption by OC, which accounts for 50% of the light absorption at 405 nm, in the high OC/SO42− episode. Idealized analysis indicates increased absorption at 781 nm by factors greater than 3 relative to denuded black carbon in the laboratory. We hypothesize that coatings of black carbon cores are the mechanism of this enhancement. This implies that climate warming and atmospheric heating rates from black carbon particles can be significantly larger than have been estimated previously. The results of this study demonstrate ways in which atmospheric processing and mixing can amplify particle light absorption for carbonaceous aerosol, significantly at short wavelength, underscoring the need to understand and predict chemical composition effects on optical properties to accurately estimate the climate radiative forcing by mixed carbonaceous aerosols.
GOMOS ozone profile validation using ground-based and balloon sonde measurements

The validation of ozone profiles retrieved by satellite instruments through comparison with data from ground-based instruments is important to monitor the evolution of the satellite instrument, to assist algorithm development and to allow multi-mission trend analyses. In this study we compare ozone profiles derived from GOMOS night-time observations with measurements from lidar, microwave radiometer and balloon sonde. Collocated pairs are analysed for dependence on several geophysical and instrument observational parameters. Validation results are presented for the operational ESA level 2 data (GOMOS version 5.00) obtained during nearly seven years of observations and a comparison using a smaller dataset from the previous processor (version 4.02) is also included. The profiles obtained from dark limb measurements (solar zenith angle >107°) when the provided processing flag is properly considered match the ground-based measurements within ±2 percent over the altitude range 20 to 40 km. Outside this range, the pairs start to deviate more and there is a latitudinal dependence: in the polar region where there is a higher amount of straylight contamination, differences start to occur lower in the mesosphere than in the tropics, whereas for the lower part of the stratosphere the opposite happens: the profiles in the tropics reach less far down as the signal reduces faster because of the higher altitude at which the maximum ozone concentration is found compared to the mid and polar latitudes. Also the bias is shifting from mostly negative in the polar region to more positive in the tropics Profiles measured under "twilight" conditions are often matching the ground-based measurements very well, but care has to be taken in all cases when dealing with "straylight" contaminated profiles. For the selection criteria applied here (data within 800 km, 3 degrees in equivalent latitude, 20 h (5 h above 50 km) and a relative ozone error in the GOMOS data of 20% or less), no dependence was found on stellar magnitude, star temperature, nor the azimuth angle of the line of sight. No evidence of a temporal trend was seen either in the bias or frequency of outliers, but a comparison applying less strict data selection criteria might show differently.
Characterising aerosol transport into the Canadian High Arctic using aerosol mass spectrometry and Lagrangian modelling

We report the analysis of measurements made using an aerosol mass spectrometer (AMS; Aerodyne Research Inc.) that was installed in the Polar Environment Atmospheric Research Laboratory (PEARL) in summer 2006. PEARL is located in the Canadian high Arctic at 610 m above sea level on Ellesmere Island (80° N 86° W). PEARL is unique for its remote location in the Arctic and because most of the time it is situated within the free troposphere. It is, therefore, well suited as a receptor site to study the long-range tropospheric transport of pollutants into the Arctic. Some information about the successful year-round operation of an AMS at a high Arctic site such as PEARL will be reported here, together with design considerations for reliable sampling under harsh low-temperature conditions. Computational fluid dynamics calculations were made to ensure that sample integrity was maintained while sampling air at temperatures that average −40 °C in the winter and can be as low as −55 °C. Selected AMS measurements of aerosol mass concentration, size and chemical composition recorded during the months of August, September and October 2006 will be reported. The air temperature was raised to about 20 °C during sampling, but the short residence time in the inlet system (~25 s) ensured that less than 10% of semivolatiles such as ammonium nitrate were lost. During this period, sulfate was, at most times, the predominant aerosol component with on average 0.115 μg m−3 (detection limit 0.003 μg m−3). The second most abundant component was undifferentiated organic aerosol, with on average 0.11 μg m−3 (detection limit 0.04 μg m−3). The nitrate component, which averaged 0.007 μg m−3, was above its detection limit (0.002 μg m−3), whereas the ammonium ion had an apparent average concentration of 0.02 μg m−3, which was approximately equal to its detection limit. A few episodes, having increased mass concentrations and lasting from several hours to several days, are apparent in the data. These were investigated further using a statistical analysis to determine their common characteristics. High correlations among some of the components arriving during the short-term episodes provide evidence for common sources. Lagrangian methods were also used to identify the source regions for some of the episodes. In all cases, these coincided with the arrival of air that had contacted the surface at latitudes below about 60° N. Most of these lower-latitude footprints were on land, but sulfate emissions from shipping in the Atlantic were also detected. The Lagrangian results demonstrate that there is direct transport of polluted air into the high Arctic (up to 80° N) from latitudes down to 40° N on a time scale of 2–3 weeks. The polluted air originates in a wide variety of industrial, resource extraction and petroleum-related activity as well as from large population centres.