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Improved satellite retrievals of NO2 and SO2 over the Canadian oil sands and comparisons with surface measurements

Satellite remote sensing is increasingly being used to monitor air quality over localized sources such as the Canadian oil sands. Following an initial study, significantly low biases have been identified in current NO2 and SO2 retrieval products from the Ozone Monitoring Instrument (OMI) satellite sensor over this location resulting from a combination of its rapid development and small spatial scale. Air mass factors (AMFs) used to convert line-of-sight "slant" columns to vertical columns were re-calculated for this region based on updated and higher resolution input information including absorber profiles from a regional-scale (15 km × 15 km resolution) air quality model, higher spatial and temporal resolution surface reflectivity, and an improved treatment of snow. The overall impact of these new Environment Canada (EC) AMFs led to substantial increases in the peak NO2 and SO2 average vertical column density (VCD), occurring over an area of intensive surface mining, by factors of 2 and 1.4, respectively, relative to estimates made with previous AMFs. Comparisons are made with long-term averages of NO2 and SO2 (2005–2011) from in situ surface monitors by using the air quality model to map the OMI VCDs to surface concentrations. This new OMI-EC product is able to capture the spatial distribution of the in situ instruments (slopes of 0.65 to 1.0, correlation coefficients of >0.9). The concentration absolute values from surface network observations were in reasonable agreement, with OMI-EC NO2 and SO2 biased low by roughly 30%. Several complications were addressed including correction for the interference effect in the surface NO2 instruments and smoothing and clear-sky biases in the OMI measurements. Overall these results highlight the importance of using input information that accounts for the spatial and temporal variability of the location of interest when performing retrievals.
Atmospheric parameters in a subtropical cloud regime transition derived by AIRS and MODIS: observed statistical variability compared to ERA-Interim

Cloud occurrence, microphysical and optical properties, and atmospheric profiles within a subtropical cloud regime transition in the northeastern Pacific Ocean are obtained from a synergistic combination of the Atmospheric Infrared Sounder (AIRS) and the MODerate resolution Imaging Spectroradiometer (MODIS). The observed cloud parameters and atmospheric thermodynamic profile retrievals are binned by cloud type and analyzed based on their probability density functions (PDFs). Comparison of the PDFs to data from the European Centre for Medium Range Weather Forecasting reanalysis (ERA-Interim) shows a strong difference in the occurrence of the different cloud types compared to clear sky. An increasing non-Gaussian behavior is observed in cloud optical thickness (τc), effective radius (re) and cloud-top temperature (Tc) distributions from stratocumulus to trade cumulus, while decreasing values of lower-tropospheric stability are seen. However, variations in the mean, width and shape of the distributions are found. The AIRS potential temperature (θ) and water vapor (q) profiles in the presence of varying marine boundary layer (MBL) cloud types show overall similarities to the ERA-Interim in the mean profiles, but differences arise in the higher moments at some altitudes. The differences between the PDFs from AIRS+MODIS and ERA-Interim make it possible to pinpoint systematic errors in both systems and help to understand joint PDFs of cloud properties and coincident thermodynamic profiles from satellite observations.
Multi-decadal aerosol variations from 1980 to 2009: a perspective from observations and a global model

Aerosol variations and trends over different land and ocean regions from 1980 to 2009 are analyzed with the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model and observations from multiple satellite sensors and available ground-based networks. Excluding time periods with large volcanic influence, aerosol optical depth (AOD) and surface concentration over polluted land regions generally vary with anthropogenic emissions, but the magnitude of this association can be dampened by the presence of natural aerosols, especially dust. Over the 30-year period in this study, the largest reduction in aerosol levels occurs over Europe, where AOD has decreased by 40–60% on average and surface sulfate concentrations have declined by a factor of up to 3–4. In contrast, East Asia and South Asia show AOD increases, but the relatively high level of dust aerosols in Asia reduces the correlation between AOD and pollutant emission trends. Over major dust source regions, model analysis indicates that the change of dust emissions over the Sahara and Sahel has been predominantly driven by the change of near-surface wind speed, but over Central Asia it has been largely influenced by the change of the surface wetness. The decreasing dust trend in the North African dust outflow region of the tropical North Atlantic and the receptor sites of Barbados and Miami is closely associated with an increase of the sea surface temperature in the North Atlantic. This temperature increase may drive the decrease of the wind velocity over North Africa, which reduces the dust emission, and the increase of precipitation over the tropical North Atlantic, which enhances dust removal during transport. Despite significant trends over some major continental source regions, the model-calculated global annual average AOD shows little change over land and ocean in the past three decades, because opposite trends in different land regions cancel each other out in the global average, and changes over large open oceans are negligible. This highlights the necessity for regional-scale assessment of aerosols and their climate impacts, as global-scale average values can obscure important regional changes.
Oligomer formation within secondary organic aerosols: equilibrium and dynamic considerations

We present a model based on the volatility basis set to consider the potential influence of oligomer content on volatility driven secondary organic aerosol (SOA) yields. The implications for aerosol evaporation studies, including dilution, chamber thermo-equilibration, and thermodenuder studies, are also considered. A simplified description of oligomer formation reproduces essentially all of the broad classes of equilibrium and dynamical observations related to SOA formation and evaporation: significant oligomer content may be consistent with mass yields that increase with organic aerosol mass concentration; reversible oligomerization can explain the hysteresis between the rate of SOA formation and its evaporation rate upon dilution; and the model is consistent with both chamber thermo-equilibration studies and thermodenuder studies of SOA evaporation.
Technical Note: An empirical algorithm estimating dry deposition velocity of fine, coarse and giant particles

An empirical algorithm is developed for calculating bulk dry deposition velocity (Vd) of fine (PM2.5) – particles having a diameter of ≤ 2.5 μm), coarse (PM2.5−10 – particles having a diameter of 2.5–10 μm), and giant (PM10+ – particles having a diameter of > 10 μm) atmospheric particles. The algorithm is developed from an empirical fit of Vd data calculated using the size-resolved Vd scheme of Zhang et al. (2001) with assumed lognormal size distributions of PM2.5, PM2.5−10 and PM10+. In the new algorithm, the surface deposition velocity (Vds) is parameterized as a simple linear function of friction velocity (u*) for PM2.5 and as a polynomial function of u* for both PM2.5−10 and PM10+ over all the 26 land use categories (LUCs). An adjustment factor as an exponential function of u* and leaf area index (LAI) is also applied to Vds of PM2.5−10 and PM10+ over 9 of the 26 LUCs that have variable LAI. Constant gravitational settling velocities are provided for PM2.5, PM2.5−10 and PM10+. Aerodynamic resistance between a reference height and the surface can be calculated using available analytical formulas from the literature. The bulk Vd of PM2.5, PM2.5−10 and PM10+ at the reference height can then be calculated by combining the gravitational settling velocity, aerodynamic resistance and the parameterized Vds. Vd values calculated using the new algorithm are within ±20% of those using the original size-resolved scheme for fine, coarse and giant particles. Uncertainties in Vd values from the new algorithm due to the pre-assumed size distributions are on the order of 20% for fine particles and on the order of a factor of 2.0 for coarse and giant particles. The new algorithm provides an alternative approach for calculating Vd of bulk aerosol particles. Vd of any particulate species can be simply estimated using this scheme as long as the mass fractions in fine, coarse and giant particles are known or can be assumed.
Numerical analysis of the chemical kinetic mechanisms of ozone depletion and halogen release in the polar troposphere

The role of halogen species (e.g., Br, Cl) in the troposphere of polar regions has been investigated since the discovery of their importance for boundary layer ozone destruction in the polar spring about 25 years ago. Halogen species take part in an auto-catalytic chemical reaction cycle, which releases Br2 and BrCl from the sea salt aerosols, fresh sea ice or snowpack, leading to ozone depletion. In this study, three different chemical reaction schemes are investigated: a bromine-only reaction scheme, which then is subsequently extended to include nitrogen-containing compounds and chlorine species and corresponding chemical reactions. The importance of specific reactions and their rate constants is identified by a sensitivity analysis. The heterogeneous reaction rates are parameterized by considering the aerodynamic resistance, a reactive surface ratio, β, i.e., the ratio of reactive surface area to total ground surface area, and the boundary layer height, Lmix. It is found that for β = 1, a substantial ozone decrease occurs after five days and ozone depletion lasts for 40 h for Lmix = 200 m. For about β ≥ 20, the time required for major ozone depletion ([O3] < 4 ppb) to occur becomes independent of the height of the boundary layer, and for β = 100 it approaches two days, 28 h of which are attributable to the induction and 20 h to the depletion time. In polar regions, a small amount of NOx may exist, which stems from nitrate contained in the snow, and may have a strong impact on the ozone depletion. Therefore, the role of nitrogen-containing species on the ozone depletion rate is studied. The results show that the NOx concentrations are influenced by different chemical reactions over different time periods. During ozone depletion, the reaction cycle involving the BrONO2 hydrolysis is dominant. A critical value of 0.0004 of the uptake coefficient of the BrONO2 hydrolysis reaction at the aerosol and saline surfaces is identified, beyond which the existence of NOx species accelerates the ozone depletion event, whereas for lower values, deceleration occurs.
A new data set of soil mineralogy for dust-cycle modeling

The mineralogy of airborne dust affects the impact of dust particles on direct and indirect radiative forcing, on atmospheric chemistry and on biogeochemical cycling. It is determined partly by the mineralogy of the dust-source regions and partly by size-dependent fractionation during erosion and transport. Here we present a data set that characterizes the clay and silt-sized fractions of global soil units in terms of the abundance of 12 minerals that are important for dust–climate interactions: quartz, feldspars, illite, smectite, kaolinite, chlorite, vermiculite, mica, calcite, gypsum, hematite and goethite. The basic mineralogical information is derived from the literature, and is then expanded following explicit rules, in order to characterize as many soil units as possible. We present three alternative realizations of the mineralogical maps, taking the uncertainties in the mineralogical data into account. We examine the implications of the new database for calculations of the single scattering albedo of airborne dust and thus for dust radiative forcing.
Secondary organic aerosol formation during June 2010 in Central Europe: measurements and modelling studies with a mixed thermodynamic-kinetic approach

Until recently secondary organic carbon aerosol (SOA) mass concentrations have been systematically underestimated by three-dimensional atmospheric-chemistry-aerosol models. With a newly proposed concept of aging of organic vapours, more realistic model results for organic carbon aerosol mass concentrations can be achieved. Applying a mixed thermodynamic-kinetic approach for SOA formation shifted the aerosol size distribution towards particles in the cloud condensation nuclei size range, thereby emphasising the importance of SOA formation schemes for modelling realistic cloud and precipitation formation. The additional importance of hetero-molecular nucleation between H2SO4 and organic vapours remains to be evaluated in three-dimensional atmospheric-chemistry-aerosol models. Here a case study is presented focusing on Puy-de-Dôme, France in June 2010. The measurements indicate a considerable increase in SOA mass concentration during the measurement campaign, which could be reproduced by modelling using a simplified thermodynamic-kinetic approach for SOA formation and increased biogenic volatile organic compound (VOC) precursor emissions. Comparison with a thermodynamic SOA formation approach shows a huge improvement in modelled SOA mass concentration with the thermodynamic-kinetic approach for SOA formation. SOA mass concentration increases by a factor of up to 6 accompanied by a slight improvement of modelled particle size distribution. Even though nucleation events at Puy-de-Dôme were rare during the chosen period of investigation, a weak event in the boundary layer could be reproduced by the model in a sensitivity study when nucleation of low-volatile secondary organic vapour is included. Differences in the model results with and without nucleation of organic vapour are visible in the lower free troposphere over several days. Taking into account the nucleation of organic vapour leads to an increase in accumulation mode particles due to coagulation and condensational growth of nucleation and Aitken mode particles.
An MCM modeling study of nitryl chloride (ClNO2) impacts on oxidation, ozone production and nitrogen oxide partitioning in polluted continental outflow

Nitryl chloride (ClNO2) is produced at night by reactions of dinitrogen pentoxide (N2O5) on chloride containing surfaces. ClNO2 is photolyzed during the morning hours after sunrise to liberate highly reactive chlorine atoms (Cl·). This chemistry takes place primarily in polluted environments where the concentrations of N2O5 precursors (nitrogen oxide radicals and ozone) are high, though it likely occurs in remote regions at lower intensities. Recent field measurements have illustrated the potential importance of ClNO2 as a daytime Cl· source and a nighttime NOx reservoir. However, the fate of the Cl· and the overall impact of ClNO2 on regional photochemistry remain poorly constrained by measurements and models. To this end, we have incorporated ClNO2 production, photolysis, and subsequent Cl· reactions into an existing master chemical mechanism (MCM version 3.2) box model framework using observational constraints from the CalNex 2010 field study. Cl· reactions with a set of alkenes and alcohols, and the simplified multiphase chemistry of N2O5, ClNO2, HOCl, ClONO2, and Cl2, none of which are currently part of the MCM, have been added to the mechanism. The presence of ClNO2 produces significant changes to oxidants, ozone, and nitrogen oxide partitioning, relative to model runs excluding ClNO2 formation. From a nighttime maximum of 1.5 ppbv ClNO2, the daytime maximum Cl· concentration reaches 1 × 105 atoms cm−3 at 07:00 model time, reacting mostly with a large suite of volatile organic compounds (VOC) to produce 2.2 times more organic peroxy radicals in the morning than in the absence of ClNO2. In the presence of several ppbv of nitrogen oxide radicals (NOx = NO + NO2), these perturbations lead to similar enhancements in hydrogen oxide radicals (HOx = OH + HO2). Neglecting contributions from HONO, the total integrated daytime radical source is 17% larger when including ClNO2, which leads to a similar enhancement in integrated ozone production of 15%. Detectable levels (tens of pptv) of chlorine containing organic compounds are predicted to form as a result of Cl· addition to alkenes, which may be useful in identifying times of active Cl· chemistry.
Surface response to rain events throughout the West African monsoon

This study analyses the response of the continental surface to rain events, taking advantage of the long-term near-surface measurements over different vegetation types at different latitudes, acquired during the African Monsoon Multidisciplinary Analysis (AMMA) by the AMMA-CATCH observing system. The simulated surface response by nine land surface models involved in AMMA Land Model Intercomparison Project (ALMIP), is compared to the observations. The surface response, described via the evaporative fraction (EF), evolves in two steps: the immediate surface response (corresponding to an increase of EF occurring immediately after the rain) and the surface recovery (characterized by a decrease of EF over several days after the rain). It is shown that, for all the experimental sites, the immediate surface response is mainly dependent on the soil moisture content and the recovery period follows an exponential relationship whose rate is strongly dependent on the vegetation type (from 1 day over bare soil to 70 days over forest) and plant functional type (below and above 10 days for annual and perennial plants, respectively). The ALMIP model ensemble depicts a broad range of relationships between EF and soil moisture, with the worst results for the drier sites (high latitudes). The land surface models tend to simulate a realistic surface recovery for vegetated sites, but a slower and more variable EF decrease is simulated over bare soil than observed.