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

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 (α) 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, α, 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, α, 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, α, and UVAI. This result suggests that remotely sensed data are not an appropriate surrogate for ground air quality in metropolitan South Africa.
Modeling the feedback between aerosol and meteorological variables in the atmospheric boundary layer during a severe fog–haze event over the North China Plain

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

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

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.
Hydroxy nitrate production in the OH-initiated oxidation of alkenes

Alkenes are oxidized rapidly in the atmosphere by addition of OH and subsequently O2 leading to the formation of β-hydroxy peroxy radicals. These peroxy radicals react with NO to form β-hydroxy nitrates with a branching ratio α. We quantify α for C2–C8 alkenes at 295 K ± 3 and 993 hPa. The branching ratio can be expressed as α = (0.045 ± 0.016) × N − (0.11 ± 0.05) where N is the number of heavy atoms (excluding the peroxy moiety), and listed errors are 2σ. These branching ratios are larger than previously reported and are similar to those for peroxy radicals formed from H abstraction from alkanes. We find the isomer distributions of β-hydroxy nitrates formed under NO-dominated peroxy radical chemistry to be different than the isomer distribution of hydroxy hydroperoxides produced under HO2-dominated peroxy radical chemistry. Assuming unity yield for the hydroperoxides implies that the branching ratio to form β-hydroxy nitrates increases with substitution of RO2. Deuterium substitution enhances the branching ratio to form hydroxy nitrates in both propene and isoprene by a factor of ~ 1.5. The role of alkene chemistry in the Houston region is re-evaluated using the RONO2 branching ratios reported here. Small alkenes are found to play a significant role in present-day oxidant formation more than a decade (2013) after the 2000 Texas Air Quality Study identified these compounds as major contributors to photochemical smog in Houston.
Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Guangzhou, and Beijing are surrounded by densely forested areas, and recent research has consistently demonstrated the importance of biogenic volatile organic compounds (VOCs) from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical, undermine our ability to assess regional photochemical air pollution problems. We present an observational data set of CO, NOx, SO2, ozone, HONO, and VOCs (anthropogenic and biogenic) from Taehwa research forest (TRF) near the Seoul metropolitan area in early June 2012. The data show that TRF is influenced both by aged pollution and fresh biogenic volatile organic compound emissions. With the data set, we diagnose HOx (OH, HO2, and RO2) distributions calculated using the University of Washington chemical box model (UWCM v2.1) with near-explicit VOC oxidation mechanisms from MCM v3.2 (Master Chemical Mechanism). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that (1) different model simulation scenarios cause systematic differences in HOx distributions, especially OH levels (up to 2.5 times), and (2) radical destruction (HO2 + HO2 or HO2 + RO2) could be more efficient than radical recycling (RO2 + NO), especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone–VOC–NOx sensitivity and VOC oxidation product formation rates. Overall, the NOx limited regime is assessed except for the morning hours (8 a.m. to 12 p.m. local standard time), but the degree of sensitivity can significantly vary depending on the model scenarios. The model results also suggest that RO2 levels are positively correlated with oxygenated VOCs (OVOCs) production that is not routinely constrained by observations. These unconstrained OVOCs can cause higher-than-expected OH loss rates (missing OH reactivity) and secondary organic aerosol formation. The series of modeling experiments constrained by observations strongly urge observational constraint of the radical pool to enable precise understanding of regional photochemical pollution problems in the East Asian megacity region.
Quantifying pyroconvective injection heights using observations of fire energy: sensitivity of spaceborne observations of carbon monoxide

We use observations of active fire area and fire radiative power (FRP) from the NASA Moderate Resolution Imaging Spectroradiometers (MODIS), together with a parameterized plume rise model, to estimate biomass burning injection heights during 2006. We use these injection heights in the GEOS-Chem (Goddard Earth Observing System Chemistry) atmospheric chemistry transport model to vertically distribute biomass burning emissions of carbon monoxide (CO) and to study the resulting atmospheric distribution. For 2006, we use over half a million FRP and fire area observations as input to the plume rise model. We find that convective heat fluxes and active fire area typically lie in the range of 1–100 kW m−2 and 0.001–100 ha, respectively, although in rare circumstances the convective heat flux can exceed 500 kW m−2. The resulting injection heights have a skewed probability distribution with approximately 80% of the injections remaining within the local boundary layer (BL), with occasional injection height exceeding 8 km. We do not find a strong correlation between the FRP-inferred surface convective heat flux and the resulting injection height, with environmental conditions often acting as a barrier to rapid vertical mixing even where the convective heat flux and active fire area are large. We also do not find a robust relationship between the underlying burnt vegetation type and the injection height. We find that CO columns calculated using the MODIS-inferred injection height (MODIS-INJ) are typically −9 to +6% different to the control calculation in which emissions are emitted into the BL, with differences typically largest over the point of emission. After applying MOPITT (Measurement of Pollution in the Troposphere) v5 scene-dependent averaging kernels we find that we are much less sensitive to our choice of injection height profile. The differences between the MOPITT and the model CO columns (max bias ~ 50%), due largely to uncertainties in emission inventories, are much larger than those introduced by the injection heights. We show that including a realistic diurnal variation in FRP (peaking in the afternoon) or accounting for subgrid-scale emission errors does not alter our main conclusions. Finally, we use a Bayesian maximum a posteriori approach constrained by MOPITT CO profiles to estimate the CO emissions but because of the inherent bias between model and MOPITT we find little impact on the resulting emission estimates. Studying the role of pyroconvection in the distribution of gases and particles in the atmosphere using global MOPITT CO observations (or any current spaceborne measurement of the atmosphere) is still associated with large errors, with the exception of a small subset of large fires and favourable environmental conditions, which will consequently lead to a bias in any analysis on a global scale.
Near-highway aerosol and gas-phase measurements in a high-diesel environment

Diesel-powered passenger cars currently outnumber gasoline-powered cars in many countries, particularly in Europe. In France, diesel cars represented 61% of light duty vehicles in 2011 and this percentage is still increasing (French Environment and Energy Management Agency, ADEME). As part of the September 2011 joint PM-DRIVE (Particulate Matter – DiRect and Indirect on-road Vehicular Emissions) and MOCOPO (Measuring and mOdeling traffic COngestion and POllution) field campaign, the concentration and high-resolution chemical composition of aerosols and volatile organic carbon species were measured adjacent to a major urban highway south of Grenoble, France. Alongside these atmospheric measurements, detailed traffic data were collected from nearby traffic cameras and loop detectors, which allowed the vehicle type, traffic concentration, and traffic speed to be quantified. Six aerosol age and source profiles were resolved using the positive matrix factorization model on real-time high-resolution aerosol mass spectra. These six aerosol source/age categories included a hydrocarbon-like organic aerosol (HOA) commonly associated with primary vehicular emissions, a nitrogen-containing aerosol with a diurnal pattern similar to that of HOA, oxidized organic aerosol (OOA), and biomass burning aerosol. While quantitatively separating the influence of diesel from that of gasoline proved impossible, a low HOA : black carbon ratio, similar to that measured in other high-diesel environments, and high levels of NOx, also indicative of diesel emissions, were observed. Although the measurement site was located next to a large source of primary emissions, which are typically found to have low oxygen incorporation, OOA was found to comprise the majority of the measured organic aerosol, and isotopic analysis showed that the measured OOA contained mainly modern carbon, not fossil-derived carbon. Thus, even in this heavily vehicular-emission-impacted environment, photochemical processes, biogenic emissions, and aerosol oxidation dominated the overall organic aerosol mass measured during most of the campaign.
Seasonal variability of Saharan desert dust and ice nucleating particles over Europe

Dust aerosols are thought to be the main contributor to atmospheric ice nucleation. While there are case studies supporting this, a climatological sense of the importance of dust to atmospheric ice nucleating particle (INP) concentrations and its seasonal variability over Europe is lacking. Here, we use a mesoscale model to estimate Saharan dust concentrations over Europe in 2008. There are large differences in median dust concentrations between seasons, with the highest concentrations and highest variability in the lower to mid-troposphere. Laboratory-based ice nucleation parameterisations are applied to these simulated dust number concentrations to calculate the potential INP resulting from immersion freezing and deposition nucleation on these dust particles. The potential INP concentrations increase exponentially with height due to decreasing temperatures in the lower and mid-troposphere. When the ice-activated fraction increases sufficiently, INP concentrations follow the dust particle concentrations. The potential INP profiles exhibit similarly large differences between seasons, with the highest concentrations in spring (median potential immersion INP concentrations nearly 105 m−3, median potential deposition INP concentrations at 120% relative humidity with respect to ice over 105 m−3), about an order of magnitude larger than those in summer. Using these results, a best-fit function is provided to estimate the potential INPs for use in limited-area models, which is representative of the normal background INP concentrations over Europe. A statistical evaluation of the results against field and laboratory measurements indicates that the INP concentrations are in close agreement with observations.
Characterization of satellite-based proxies for estimating nucleation mode particles over South Africa

Proxies for estimating nucleation mode number concentrations and further simplification for their use with satellite data have been presented in Kulmala et al. (2011). In this paper we discuss the underlying assumptions for these simplifications and evaluate the resulting proxies over an area in South Africa based on a comparison with a suite of ground-based measurements available from four different stations. The proxies are formulated in terms of sources (concentrations of precursor gases (NO2 and SO2) and UVB radiation intensity near the surface) and a sink term related to removal of the precursor gases due to condensation on pre-existing aerosols. A-Train satellite data are used as input to compute proxies. Both the input data and the resulting proxies are compared with those obtained from ground-based measurements. In particular, a detailed study is presented on the substitution of the local condensation sink (CS) with satellite aerosol optical depth (AOD), which is a column-integrated parameter. One of the main factors affecting the disagreement between CS and AOD is the presence of elevated aerosol layers. Overall, the correlation between proxies calculated from the in situ data and observed nucleation mode particle number concentrations (Nnuc) remained low. At the time of the satellite overpass (13:00–14:00 LT) the highest correlation is observed for SO2/CS (R2 = 0.2). However, when the proxies are calculated using satellite data, only NO2/AOD showed some correlation with Nnuc (R2 = 0.2). This can be explained by the relatively high uncertainties related especially to the satellite SO2 columns and by the positive correlation that is observed between the ground-based SO2 and NO2 concentrations. In fact, results show that the satellite NO2 columns compare better with in situ SO2 concentration than the satellite SO2 column. Despite the high uncertainties related to the proxies calculated using satellite data, the proxies calculated from the in situ data did not better predict Nnuc. Hence, overall improvements in the formulation of the proxies are needed.