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The transport of atmospheric NOx and HNO3 over Cape Town

Cape Town, the most popular tourist city in Africa, usually experiences air pollution with unpleasant odour in winter. Previous studies have associated the pollution with local emission of pollutants within the city. The present study examines the transport of atmospheric pollutants (NOx and HNO3) over South Africa and shows how the transport of pollutants from the Mpumalanga Highveld, a major South African industrial area, may contribute to the pollution in Cape Town. The study analysed observation data (2001–2008) from the Cape Town air-quality network and simulation data (2001–2004) from a regional climate model (RegCM) over southern Africa. The simulation accounts for the influence of complex topography, atmospheric conditions, and atmospheric chemistry on emission and transport of pollutants over southern Africa. Flux budget analysis was used to examine whether Cape Town is a source or sink for NOx and HNO3 during the extreme pollution events. The results show that extreme pollution events in Cape Town are associated with the lower level (surface – 850 hPa) transport of NOx from the Mpumalanga Highveld to Cape Town, and with a tongue of high concentration of HNO3 that extends from the Mpumalanga Highveld to Cape Town along the south coast of South Africa. The prevailing atmospheric conditions during the extreme pollution events feature an upper-level (700 hPa) anticyclone over South Africa and a lower-level col over Cape Town. The anticyclone induces a strong subsidence motion, which prevents vertical mixing of the pollutants and caps high concentration of pollutants close to the surface as they are transported from the Mpumalanga Highveld toward Cape Town. The col accumulates the pollutants over the city. This study shows that Cape Town can be a sink for the NOx and HNO3 during extreme pollution events and suggests that the accumulation of pollutants transported from other areas (e.g. the Mpumalanga Highveld) may contribute to the air pollution in Cape Town.
Pressure dependent isotopic fractionation in the photolysis of formaldehyde-d2

The isotope effects in formaldehyde photolysis are the key link between the δD of methane emissions and the δD of atmospheric in situ hydrogen production. A few recent studies have suggested that a pressure dependence in the isotopic fractionation can partly explain enrichment of deuterium with altitude in the atmosphere. The mechanism and the extent of this pressure dependency is, however, not adequately described. In the present work D2CO and H2CO were photolyzed in a static reaction chamber at bath gas pressures of 50, 200, 400, 600 and 1000 mbar; these experiments compliment and extend our earlier work with HDCO vs. H2CO. The UV lamps used for photolysis emit light at wavelengths that primarily dissociate formaldehyde into molecular products, CO and H2 or D2. The isotope effect k(H2CO)/k(D2CO) = 3.16 ± 0.03 at 1000 mbar is in good agreement with results from previous studies. Similarly to what was previously shown for k(H2CO)/k(HDCO), the isotope effect decreased as pressure decreased. In addition, a model was constructed using RRKM theory to calculate the lifetime of excited formaldehyde on the S0 surface, to investigate its role in the observed pressure dependent photolytic fractionation of deuterium. The model shows that part of the fractionation is a result of competition between the isotopologue dependent rates of unimolecular dissociation and collisional relaxation. We suggest that the remaining fractionation is due to isotope effects in the rate of the non-radiative transition from S1 to S0, which are not considered in the present model.
On the consistency between global and regional methane emissions inferred from SCIAMACHY, TANSO-FTS, IASI and surface measurements

Satellite retrievals of methane weighted atmospheric columns are assimilated within a Bayesian inversion system to infer the global and regional methane emissions and sinks for the period August 2009 to July 2010. Inversions are independently computed from three different space-borne observing systems and one surface observing system under several hypotheses for prior-flux and observation errors. Posterior methane emissions are compared and evaluated against surface mole fraction observations via a chemistry-transport model. Apart from SCIAMACHY (SCanning Imaging Absorption spectroMeter for Atmospheric CartograpHY), the simulations agree fairly well with the surface mole fractions. The most consistent configurations of this study using TANSO-FTS (Thermal And Near infrared Sensor for carbon Observation – Fourier Transform Spectrometer), IASI (Infrared Atmospheric Sounding Interferometer) or surface measurements induce posterior methane global emissions of, respectively, 565 ± 21 Tg yr−1, 549 ± 36 Tg yr−1 and 538 ± 15 Tg yr−1 over the one-year period August 2009–July 2010. This consistency between the satellite retrievals (apart from SCIAMACHY) and independent surface measurements is promising for future improvement of CH4 emission estimates by atmospheric inversions.
The role of horizontal model resolution in assessing the transport of CO in a middle latitude cyclone using WRF-Chem

We use the Weather Research and Forecasting with Chemistry (WRF-Chem) online chemical transport model to simulate a middle latitude cyclone in East Asia at three different horizontal resolutions (45, 15, and 5 km grid spacing). The cyclone contains a typical warm conveyor belt (WCB) with an embedded squall line that passes through an area having large surface concentrations (> 400 ppbv) of carbon monoxide (CO). Model output from WRF-Chem is used to compare differences between the large-scale CO vertical transport by the WCB (the 45 km simulation) with the smaller-scale transport due to its convection (the 5 km simulation). Forward trajectories are calculated from WRF-Chem output using the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model. At 45 km grid spacing, the WCB exhibits gradual ascent, lofting surface CO to 6–7 km. Upon reaching the warm front, the WCB and associated CO ascend more rapidly and later turn eastward over the Pacific Ocean. Convective transport at 5 km resolution with explicitly resolved convection occurs much more rapidly, with surface CO lofted to altitudes greater than 10 km in 1 h or less. We also compute CO vertical mass fluxes over specified areas and times to compare differences in transport due to the different grid spacings. Upward CO flux exceeds 110 000 t h−1 in the domain with explicit convection when the squall line is at peak intensity, while fluxes from the two coarser resolutions are an order of magnitude smaller. Specific areas of interest within the 5 km domain are defined to compare the magnitude of convective transport to that within the entire 5 km region. Although convection encompasses only a small portion of the 5 km domain, it is responsible for ~40% of the upward CO transport. We also examine the vertical transport due to a short wave trough and its associated area of convection, not related to the cyclone, that lofts CO to the upper troposphere. Results indicate that fine-scale resolution with explicitly resolved convection is important when assessing the vertical transport of surface emissions in areas of deep convection.
Comparing ECMWF AOD with AERONET observations at visible and UV wavelengths

This paper presents validation results of the European Centre for Medium-Range Weather Forecasts (ECMWF) Integrated Forecasting System MACC (Monitoring Atmospheric Composition and Climate) re-analysis aerosol optical depth (AOD) for the period 2003–2006. We evaluate the MACC AOD at a UV wavelength (340 nm) and at mid-visible (500 and 550 nm) by comparing against ground-based AERONET measurements at 12 sites. The AERONET sites cover various parts of the globe and are categorized in three groups: urban/anthropogenic, biomass burning and dust, depending on the typically dominating aerosol type. This is the first time a global model such as the ECMWF has been evaluated for the performance of AOD at a UV wavelength. The results show that the MACC system generally provides a good representation of the AOD on a monthly basis, showing a realistic seasonal cycle. The model is mostly able to capture major dust load events and also the peak months of biomass burning correctly. For Kanpur and Solar Village, however, the model overestimates the AOD during the monsoon period when the aerosol load is generally low. When comparing hourly AOD values, the model–measurement agreement is better for biomass burning and dust sites than for urban sites, with an average correlation coefficient around 0.90 for biomass burning sites, around 0.77 for dust sites, and below 0.70 for urban sites. The AOD at 500 nm averaged over all sites shows only a small systematic difference between modeled and measured values, with a relative mean bias of 0.02. However, for the AOD at 340 nm the relative mean bias is −0.2. All sites included in the study show a relative mean bias at 340 nm smaller (or more negative) than that at 500 nm, indicating a strong wavelength dependence in the performance of the AOD in the MACC system. A comparison against fine and coarse mode AOD of the AERONET indicates that this has to do with the size distribution of the model: generally, the ECMWF model overestimates the contribution by coarse mode particles.
Enhancement of atmospheric H2SO4 / H2O nucleation: organic oxidation products versus amines

Atmospheric H2SO4 / H2O nucleation influencing effects have been studied in the flow tube IfT-LFT (Institute for Tropospheric Research – Laminar Flow Tube) at 293 ± 0.5 K and a pressure of 1 bar using synthetic air as the carrier gas. The presence of a possible background amine concentration in the order of 107–108 molecule cm−3 throughout the experiments has to be taken into account. In a first set of investigations, ozonolysis of olefins (tetramethylethylene, 1-methyl-cyclohexene, α-pinene and limonene) for close to atmospheric concentrations, served as the source of OH radicals and possibly other oxidants initiating H2SO4 formation starting from SO2. The oxidant generation is inevitably associated with the formation of organic oxidation products arising from the parent olefins. These products (first generation mainly) showed no clear effect on the number of nucleated particles within a wide range of experimental conditions for H2SO4 concentrations higher than ~107 molecule cm−3. Also the early growth process of the nucleated particles was not significantly influenced by the organic oxidation products in line with the expected growth by organic products using literature data. An additional, H2SO4-independent process of particle (nano-CN) formation was observed in the case of α-pinene and limonene ozonolysis for H2SO4 concentrations smaller than ~107 molecule cm−3. Furthermore, the findings confirm the appearance of an additional oxidant for SO2 beside OH radicals, very likely stabilized Criegee Intermediates (sCI). A second set of experiments has been performed in the presence of added amines in the concentrations range of a few 107–1010 molecule cm−3 applying photolytic OH radical generation for H2SO4 production without addition of other organics. All amines showed significant nucleation enhancement with increasing efficiency in the order pyridine < aniline < dimethylamine < trimethylamine. This result supports the idea of H2SO4 cluster stabilization by amines due to strong H2SO4↔amine interactions. On the other hand, this study indicates that for organic oxidation products (in presence of the possible amine background as stated) a distinct H2SO4 / H2O nucleation enhancement can be due to increased H2SO4 formation caused by additional organic oxidant production (sCI) rather than by stabilization of H2SO4 clusters due to H2SO4↔organics interactions.
Observation and a numerical study of gravity waves during tropical cyclone Ivan (2008)

Gravity waves (GWs) with horizontal wavelengths of 32–2000 km are investigated during tropical cyclone (TC) Ivan (2008) in the southwest Indian Ocean in the upper troposphere (UT) and the lower stratosphere (LS) using observational data sets, radiosonde and GPS radio occultation data, ECMWF analyses and simulations of the French numerical model Meso-NH with vertical resolution < 150 m near the surface and 500 m in the UT/LS. Observations reveal dominant low-frequency GWs with short vertical wavelengths of 0.7–3 km, horizontal wavelengths of 80–400 km and periods of 4.6–13 h in the UT/LS. Continuous wavelet transform and image-processing tools highlight a wide spectrum of GWs with horizontal wavelengths of 40–1800 km, short vertical wavelengths of 0.6–3.3 km and periods of 20 min–2 days from modelling analyses. Both ECMWF and Meso-NH analyses are consistent with radiosonde and GPS radio occultation data, showing evidence of a dominant TC-related quasi-inertia GW propagating eastward east of TC Ivan with horizontal and vertical wavelengths of 400–800 km and 2–3 km respectively in the LS, more intense during TC intensification. In addition, the Meso-NH model produces a realistic, detailed description of TC dynamics, some high-frequency GWs near the TC eye, variability of the tropospheric and stratospheric background wind and TC rainband characteristics at different stages of TC Ivan. A wave number 1 vortex Rossby wave is suggested as a source of dominant inertia GW with horizontal wavelengths of 400–800 km, while shorter scale modes (100–200 km) located at northeast and southeast of the TC could be attributed to strong localized convection in spiral bands resulting from wave number 2 vortex Rossby waves. Meso-NH simulations also reveal GW-related clouds east of TC Ivan.
Elemental carbon in snow at Changbai Mountain, northeastern China: concentrations, scavenging ratios, and dry deposition velocities

Light-absorbing aerosol – particularly elemental carbon (EC) – while mixed with snow and ice is an important climate driver from the enhanced absorption of solar radiation. Currently, considerable efforts are being made to estimate its radiative forcing on a global scale, but several uncertainties remain, particularly those regarding its deposition processes. In this study, concurrent measurements of EC in air and snow are performed for three years (2009–2012) at Changbai station, northeastern China. The scavenging ratio and the wet- and dry-deposition fluxes of EC over the snow surface are estimated. The mean EC concentration in the surface snow is 1000 ± 1500 ng g−1, ranging from 7 to 7640 ng g−1. The mean value of the scavenging ratio of EC by snow is 140 ± 100, with a median value of 150, which is smaller than that reported in Arctic areas. A non-rimed snow process is a significant factor in interpreting differences with Arctic areas. Wet-deposition fluxes of EC are estimated to be 0.47 ± 0.37 μg cm−2 month−1 on average over the three snow seasons studied. Dry deposition is more than five times higher, with an average of 2.65 ± 1.93 μg cm−2 month−1; however, only winter period estimation is possible (December–February). During winter in Changbai, 87% of EC in snow is estimated to be due to dry deposition, with a mean dry deposition velocity of 6.44 × 10−3 m s−1 and median of 8.14 × 10−3 m s−1. Finally, the calculation of the radiative effect shows that 500 ng g−1 of dry-deposited EC to a snow surface absorbs three times more incoming solar energy than the same mass mixed in the snow through wet deposition. Deposition processes of an EC-containing snow surface are, therefore, crucial to estimate its radiative forcing better, particularly in northeastern China, where local emission strongly influences the level and gradient of EC in the snowpack, and snow-covered areas are cold and dry due to the atmospheric general circulation. Furthermore, this study builds on the knowledge to characterize the conditions in the snow-laden Chinese rural areas better as well as to constrain transport of EC to the Arctic better.
Flow climatology for physicochemical properties of dichotomous aerosol over the western North Atlantic Ocean at Bermuda

Dichotomous aerosols (nominal super- and sub-μm-diameter size fractions) in sectored on-shore flow were sampled daily from July 2006 through June 2009, at the Tudor Hill Atmospheric Observatory (THAO) on the western coast of Bermuda (32.27° N, 64.87° W) and analyzed for major chemical and physical properties. FLEXPART retroplumes were calculated for each sampling period and aerosol properties were stratified accordingly based on transport from different regions. Transport from the northeastern United States (NEUS) was associated with significantly higher (factors of 2 to 3 based on median values) concentrations of bulk particulate non-sea-salt (nss) SO42-, NO3-, and NH4+ and associated scattering and absorption at 530 nm, relative to transport from Africa (AFR) and the oceanic background. These differences were driven primarily by higher values associated with the sub-μm size fraction under NEUS flow. We estimate that 75(±3)% of the NEUS nss SO42- was anthropogenic in origin, while only 25(±9)% of the AFR nss SO42- was anthropogenic. Integrating over all transport patterns, the contribution of anthropogenic sulfate has dropped 14.6% from the early 1990s. Bulk scattering was highly correlated with bulk nss SO42- in all flow regimes but the corresponding regression slopes varied significantly reflecting differential contributions to total scattering by associated aerosol components. Absorption by super-μm aerosol in transport from the NEUS versus AFR was similar although the super-μm aerosol size fraction accounted for a relatively greater contribution to total absorption in AFR flow. Significantly greater absorption Ångström exponents (AAEs) for AFR flow reflects the wavelength dependence of absorption by mineral aerosols; lower AAEs for NEUS flow is consistent with the dominance of absorption by combustion-derived aerosols. Higher AOD associated with transport from both the NEUS and AFR relative to oceanic background flow results in a top of atmosphere direct radiative forcing on the order of −1.6 to −2.5 W m−2, respectively, showing these aerosols drive cooling. The dominance of transport from the NEUS on an annual basis coupled with the corresponding decreases in anthropogenic nss SO42- aerosols since the early 1990s implies that emission reductions in the US account for a decline in atmospheric cooling over the western North Atlantic Ocean during this period.
The impact of satellite-adjusted NOx emissions on simulated NOx and O3 discrepancies in the urban and outflow areas of the Pacific and Lower Middle US

We analyze the simulation results from a CMAQ model and GOME-2 NO2 retrievals over the United States for August 2009 to estimate the model-simulated biases of NOx concentrations over six geological regions (Pacific Coast = PC, Rocky Mountains = RM, Lower Middle = LM, Upper Middle = UM, Southeast = SE, Northeast = NE). By comparing GOME-2 NO2 columns to corresponding CMAQ NO2 columns, we produced satellite-adjusted NOx emission ("GOME2009") and compared baseline emission ("BASE2009") CMAQ simulations with GOME2009 CMAQ runs. We found that the latter exhibited decreases of −5.6%, −12.3%, −21.3%, and −15.9 % over the PC, RM, LM, and SE regions, respectively, and increases of +2.3% and +10.0% over the UM and NE regions. In addition, we found that changes in NOx emissions generally mitigate discrepancies between the surface NOx concentrations of baseline CMAQ and those of AQS at EPA AQS stations (mean bias of +19.8% to −13.7% over PC, −13.8% to −36.7% over RM, +149.7% to −1.8% over LM, +22.5% to −7.8% over UM, +31.3% to −7.9% over SE, and +11.6% to +0.7% over NE). The relatively high simulated NOx biases from baseline CMAQ over LM (+149.7%) are likely the results of over-predictions of simulated NOx emissions, which could shed light on those from global/regional Chemical Transport Models. We also perform more detailed investigations on surface NOx and O3 concentrations in two urban and outflow areas, PC (e.g., Los Angeles, South Pasadena, Anaheim, La Habra and Riverside) and LM (e.g., Houston, Beaumont and Sulphur). From two case studies, we found that the GOME2009 emissions decreased surface NOx concentrations significantly in the urban areas of PC (up to 30 ppbv) and in those of LM (up to 10 ppbv) during the daytime and that simulated NOx concentrations from CMAQ with GOME2009 compare well to those of in-situ AQS observations. A significant reduction in NOx concentrations resulted in a comparable increase in surface O3 concentrations in the urban areas of PC (up to 30 ppbv) and the resulting simulated O3 concentrations compare well with in-situ surface O3 observations over South Pasadena, Anaheim, and Riverside. Over Houston, Beaumont, and Sulphur, large reductions in NOx emissions from CMAQ with GOME2009 coincides with large reduced concentrations of simulated NOx. These concentrations are similar to those of the EPA AQS NOx observations. However, the resulting simulated increase in surface O3 at the urban stations in Houston and Sulphur exacerbated preexisting high O3 over-predictions of the baseline CMAQ. This study implies that simulated low O3 biases in the urban areas of PC are likely caused by simulated high NOx biases, but high O3 biases in the urban areas of LM cannot be explained by simulated high NOx biases over the region. This study also suggests that both in-situ surface NOx and O3 observations should be used simultaneously to resolve issues pertaining to simulated high/low O3 bias and that remote-sensing data could be used as a constraint for bottom-up emissions. In addition, we also found that daytime O3 reductions over the outflow regions of LM following large reductions in NOx emissions in the urban areas are significantly larger than they are over outflow regions of PC. These findings provide policymakers in the two regions with information critical to establishing strategies for mitigating air pollution.