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A detailed characterization of air quality in the megacity of Paris (France) during two 1-month intensive campaigns and from additional 1-year observations revealed that about 70 % of the urban background fine particulate matter (PM) is transported on average into the megacity from upwind regions. This dominant influence of regional sources was confirmed by in situ measurements during short intensive and longer-term campaigns, aerosol optical depth (AOD) measurements from ENVISAT, and modeling results from PMCAMx and CHIMERE chemistry transport models. While advection of sulfate is well documented for other megacities, there was surprisingly high contribution from long-range transport for both nitrate and organic aerosol. The origin of organic PM was investigated by comprehensive analysis of aerosol mass spectrometer (AMS), radiocarbon and tracer measurements during two intensive campaigns. Primary fossil fuel combustion emissions constituted less than 20 % in winter and 40 % in summer of carbonaceous fine PM, unexpectedly small for a megacity. Cooking activities and, during winter, residential wood burning are the major primary organic PM sources. This analysis suggests that the major part of secondary organic aerosol is of modern origin, i.e., from biogenic precursors and from wood burning. Black carbon concentrations are on the lower end of values encountered in megacities worldwide, but still represent an issue for air quality. These comparatively low air pollution levels are due to a combination of low emissions per inhabitant, flat terrain, and a meteorology that is in general not conducive to local pollution build-up. This revised picture of a megacity only being partially responsible for its own average and peak PM levels has important implications for air pollution regulation policies.
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In this study we attempted to better quantify radiative effects of dust over the Arabian Peninsula and their dependence on input parameters. For this purpose we have developed a stand-alone column radiation transport model coupled with the Mie, T-matrix and geometric optics calculations and driven by reanalysis meteorological fields and atmospheric composition. Numerical experiments were carried out for a wide range of aerosol optical depths, including extreme values developed during the dust storm on 18–20 March 2012. Comprehensive ground-based observations and satellite retrievals were used to estimate aerosol optical properties, validate calculations and carry out radiation closure. The broadband surface albedo, fluxes at the bottom and top of the atmosphere as well as instantaneous dust radiative forcing were estimated both from the model and observations. Diurnal cycle of the shortwave instantaneous dust direct radiative forcing was studied for a range of aerosol and surface characteristics representative of the Arabian Peninsula. Mechanisms and parameters responsible for diurnal variability of the radiative forcing were evaluated. We found that intrinsic variability of the surface albedo and its dependence on atmospheric conditions, along with anisotropic aerosol scattering, are mostly responsible for diurnal effects.
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In July 2013 very strong boreal fire plumes were observed at the northern rim of the Alps by lidar and ceilometer measurements of aerosol, ozone and water vapour for about 3 weeks. In addition, some of the lower-tropospheric components of these layers were analysed at the Global Atmosphere Watch laboratory at the Schneefernerhaus high-altitude research station (2650 m a.s.l., located a few hundred metres south-west of the Zugspitze summit). The high amount of particles confirms our hypothesis that fires in the Arctic regions of North America lead to much stronger signatures in the central European atmosphere than the multitude of fires in the USA. This has been ascribed to the prevailing anticyclonic advection pattern during favourable periods and subsidence, in contrast to warm-conveyor-belt export, rainout and dilution frequently found for lower latitudes. A high number of the pronounced aerosol structures were positively correlated with elevated ozone. Chemical ozone formation in boreal fire plumes is known to be rather limited. Indeed, these air masses could be attributed to stratospheric air intrusions descending from remote high-latitude regions, obviously picking up the aerosol on their way across Canada. In one case, subsidence from the stratosphere over Siberia over as many as 15–20 days without increase in humidity was observed although a significant amount of Canadian smoke was trapped. These coherent air streams lead to rather straight and rapid transport of the particles to Europe.
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The springtime depletion of tropospheric ozone in the Arctic is known to be caused by active halogen photochemistry resulting from halogen atom precursors emitted from snow, ice, or aerosol surfaces. The role of bromine in driving ozone depletion events (ODEs) has been generally accepted, but much less is known about the role of chlorine radicals in ozone depletion chemistry. While the potential impact of iodine in the High Arctic is more uncertain, there have been indications of active iodine chemistry through observed enhancements in filterable iodide, probable detection of tropospheric IO, and recently, observation of snowpack photochemical production of I<sub>2</sub>. Despite decades of research, significant uncertainty remains regarding the chemical mechanisms associated with the bromine-catalyzed depletion of ozone, as well as the complex interactions that occur in the polar boundary layer due to halogen chemistry. To investigate this, we developed a zero-dimensional photochemical model, constrained with measurements from the 2009 OASIS field campaign in Barrow, Alaska. We simulated a 7-day period during late March that included a full ozone depletion event lasting 3 days and subsequent ozone recovery to study the interactions of halogen radicals under these different conditions. In addition, the effects of iodine added to our Base Model were investigated. While bromine atoms were primarily responsible for ODEs, chlorine and iodine were found to enhance the depletion rates and iodine was found to be more efficient per atom at depleting ozone than Br. The interaction between chlorine and bromine is complex, as the presence of chlorine can increase the recycling and production of Br atoms, while also increasing reactive bromine sinks under certain conditions. Chlorine chemistry was also found to have significant impacts on both HO<sub>2</sub> and RO<sub>2</sub>, with organic compounds serving as the primary reaction partner for Cl atoms. The results of this work highlight the need for future studies on the production mechanisms of Br<sub>2</sub> and Cl<sub>2</sub>, as well as on the potential impact of iodine in the High Arctic.
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Measurements of equivalent black carbon (EBC) in aerosols at the high Arctic field site Villum Research Station (VRS) at Station Nord in North Greenland showed a seasonal variation in EBC concentrations with a maximum in winter and spring at ground level. Average measured concentrations were about 0.067 ± 0.071 for the winter and 0.011 ± 0.009 for the summer period. These data were obtained using a multi-angle absorption photometer (MAAP). A similar seasonal pattern was found for sulfate concentrations with a maximum level during winter and spring analyzed by ion chromatography. Here, measured average concentrations were about 0.485 ± 0.397 for the winter and 0.112 ± 0.072 for the summer period. A correlation between EBC and sulfate concentrations was observed over the years 2011 to 2013 stating a correlation coefficient of <i>R</i><sup>2</sup> = 0.72. This finding gives the hint that most likely transport of primary emitted BC particles to the Arctic was accompanied by aging of the aerosols through condensational processes. BC and sulfate are known to have only partly similar sources with respect to their transport pathways when reaching the high Arctic. Aging processes may have led to the formation of secondary inorganic matter and further transport of BC particles as cloud processing and further washout of particles is less likely based on the typically observed transport patterns of air masses arriving at VRS. Additionally, concentrations of EC (elemental carbon) based on a thermo-optical method were determined and compared to EBC measurements. EBC measurements were generally higher, but a correlation between EC and EBC resulted in a correlation coefficient of <i>R</i><sup>2</sup> = 0.64. <br><br> Model estimates of the climate forcing due to BC in the Arctic are based on contributions of long-range transported BC during spring and summer. The measured concentrations were here compared with model results obtained by the Danish Eulerian Hemispheric Model, DEHM. Good agreement between measured and modeled concentrations of both EBC/BC and sulfate was observed. Also, the correlation between BC and sulfate concentrations was confirmed based on the model results observed over the years 2011 to 2013 stating a correlation coefficient of <i>R</i><sup>2</sup> = 0.74. The dominant source is found to be combustion of fossil fuel with biomass burning as a minor, albeit significant source.
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The important task to observe the global coverage of middle atmospheric trace gases like water vapor or ozone usually is accomplished by satellites. Climate and atmospheric studies rely upon the knowledge of trace gas distributions throughout the stratosphere and mesosphere. Many of these gases are currently measured from satellites, but it is not clear whether this capability will be maintained in the future. This could lead to a significant knowledge gap of the state of the atmosphere. We explore the possibilities of mapping middle atmospheric water vapor in the Northern Hemisphere by using Lagrangian trajectory calculations and water vapor profile data from a small network of five ground-based microwave radiometers. Four of them are operated within the frame of NDACC (Network for the Detection of Atmospheric Composition Change). Keeping in mind that the instruments are based on different hardware and calibration setups, a height-dependent bias of the retrieved water vapor profiles has to be expected among the microwave radiometers. In order to correct and harmonize the different data sets, the Microwave Limb Sounder (MLS) on the Aura satellite is used to serve as a kind of traveling standard. A domain-averaging TM (trajectory mapping) method is applied which simplifies the subsequent validation of the quality of the trajectory-mapped water vapor distribution towards direct satellite observations. Trajectories are calculated forwards and backwards in time for up to 10 days using 6 hourly meteorological wind analysis fields. Overall, a total of four case studies of trajectory mapping in different meteorological regimes are discussed. One of the case studies takes place during a major sudden stratospheric warming (SSW) accompanied by the polar vortex breakdown; a second takes place after the reformation of stable circulation system. TM cases close to the fall equinox and June solstice event from the year 2012 complete the study, showing the high potential of a network of ground-based remote sensing instruments to synthesize hemispheric maps of water vapor.
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Air quality measurements at Look Rock, Tennessee – on the western edge of the Great Smoky Mountains National Park – were begun in 1980 and expanded during the 1980s to a National Park Service (NPS) IMPROVE network station. Measurements were expanded again by the Tennessee Valley Authority (TVA, 1999–2007) to examine the effects of electric generating unit (EGU) emission reductions of SO<sub>2</sub> and NO<sub><i>x</i></sub> on air quality at the station. Analysis of temporal trends (1999–2013) has been conducted at the site in collaboration with activities related to the 2013 Southeast Atmosphere Study (SAS) at Look Rock and other southeastern US locations. <br><br> Key findings from these trend studies include the observation that primary pollutant levels have consistently tracked emission reductions from EGUs and other primary sources in the region, but reductions in secondary pollutants such as particulate sulfate and, specifically, ozone have been smaller compared to reductions in primary emissions. Organic carbonaceous material (OM) remains a major contributor (30–40 % in the period 2009–2013) to fine particulate mass at the site, as confirmed by ACSM measurements at the site in 2013. A large portion (65–85 %) of carbon in OM derives from modern carbon sources based on <sup>14</sup>C measurements. Important parameters affecting ozone levels, fine mass, and visibility also include the specific diurnal meteorology at this ridge-top site, its location in a predominantly mixed-deciduous forest, and the presence of primary sources of precursors at distances of 50–500 km from the site in all directions.
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With the densification of surface observing networks and the development of remote sensing of greenhouse gases from space, estimations of methane (CH<sub>4</sub>) sources and sinks by inverse modeling are gaining additional constraining data but facing new challenges. The chemical transport model (CTM) linking the flux space to methane mixing ratio space must be able to represent these different types of atmospheric constraints for providing consistent flux estimations. <br><br> Here we quantify the impact of sub-grid-scale physical parameterization errors on the global methane budget inferred by inverse modeling. We use the same inversion setup but different physical parameterizations within one CTM. Two different schemes for vertical diffusion, two others for deep convection, and one additional for thermals in the planetary boundary layer (PBL) are tested. Different atmospheric methane data sets are used as constraints (surface observations or satellite retrievals). <br><br> At the global scale, methane emissions differ, on average, from 4.1 Tg CH<sub>4</sub> per year due to the use of different sub-grid-scale parameterizations. Inversions using satellite total-column mixing ratios retrieved by GOSAT are less impacted, at the global scale, by errors in physical parameterizations. Focusing on large-scale atmospheric transport, we show that inversions using the deep convection scheme of Emanuel (1991) derive smaller interhemispheric gradients in methane emissions, indicating a slower interhemispheric exchange. At regional scale, the use of different sub-grid-scale parameterizations induces uncertainties ranging from 1.2 % (2.7 %) to 9.4 % (14.2 %) of methane emissions when using only surface measurements from a background (or an extended) surface network. Moreover, spatial distribution of methane emissions at regional scale can be very different, depending on both the physical parameterizations used for the modeling of the atmospheric transport and the observation data sets used to constrain the inverse system. <br><br> When using only satellite data from GOSAT, we show that the small biases found in inversions using a coarser version of the transport model are actually masking a poor representation of the stratosphere–troposphere methane gradient in the model. Improving the stratosphere–troposphere gradient reveals a larger bias in GOSAT CH<sub>4</sub> satellite data, which largely amplifies inconsistencies between the surface and satellite inversions. A simple bias correction is proposed. The results of this work provide the level of confidence one can have for recent methane inversions relative to physical parameterizations included in CTMs.
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Data assimilation systems allow for estimating surface fluxes of greenhouse gases from atmospheric concentration measurements. Good knowledge about fluxes is essential to understand how climate change affects ecosystems and to characterize feedback mechanisms. Based on the assimilation of more than 1 year of atmospheric in situ concentration measurements, we compare the performance of two established data assimilation models, CarbonTracker and TM5-4DVar (Transport Model 5 – Four-Dimensional Variational model), for CO<sub>2</sub> flux estimation. CarbonTracker uses an ensemble Kalman filter method to optimize fluxes on ecoregions. TM5-4DVar employs a 4-D variational method and optimizes fluxes on a 6° × 4° longitude–latitude grid. Harmonizing the input data allows for analyzing the strengths and weaknesses of the two approaches by direct comparison of the modeled concentrations and the estimated fluxes. We further assess the sensitivity of the two approaches to the density of observations and operational parameters such as the length of the assimilation time window. <br><br> Our results show that both models provide optimized CO<sub>2</sub> concentration fields of similar quality. In Antarctica CarbonTracker underestimates the wintertime CO<sub>2</sub> concentrations, since its 5-week assimilation window does not allow for adjusting the distant surface fluxes in response to the detected concentration mismatch. Flux estimates by CarbonTracker and TM5-4DVar are consistent and robust for regions with good observation coverage, regions with low observation coverage reveal significant differences. In South America, the fluxes estimated by TM5-4DVar suffer from limited representativeness of the few observations. For the North American continent, mimicking the historical increase of the measurement network density shows improving agreement between CarbonTracker and TM5-4DVar flux estimates for increasing observation density.
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Ground- and satellite-based measurements have reported high concentrations of iodine monoxide (IO) in coastal Antarctica. The sources of such a large iodine burden in the coastal Antarctic atmosphere remain unknown. We propose a mechanism for iodine release from sea ice based on the premise that micro-algae are the primary source of iodine emissions in this environment. The emissions are triggered by the biological production of iodide (I<sup>−</sup>) and hypoiodous acid (HOI) from micro-algae (contained within and underneath sea ice) and their diffusion through sea-ice brine channels, ultimately accumulating in a thin brine layer (BL) on the surface of sea ice. Prior to reaching the BL, the diffusion timescale of iodine within sea ice is depth-dependent. The BL is also a vital component of the proposed mechanism as it enhances the chemical kinetics of iodine-related reactions, which allows for the efficient release of iodine to the polar boundary layer. We suggest that iodine is released to the atmosphere via three possible pathways: (1) emitted from the BL and then transported throughout snow atop sea ice, from where it is released to the atmosphere; (2) released directly from the BL to the atmosphere in regions of sea ice that are not covered with snowpack; or (3) emitted to the atmosphere directly through fractures in the sea-ice pack. To investigate the proposed biology–ice–atmosphere coupling at coastal Antarctica we use a multiphase model that incorporates the transport of iodine species, via diffusion, at variable depths, within brine channels of sea ice. Model simulations were conducted to interpret observations of elevated springtime IO in the coastal Antarctic, around the Weddell Sea. While a lack of experimental and observational data adds uncertainty to the model predictions, the results nevertheless show that the levels of inorganic iodine (i.e. I<sub>2</sub>, IBr, ICl) released from sea ice through this mechanism could account for the observed IO concentrations during this timeframe. The model results also indicate that iodine may trigger the catalytic release of bromine from sea ice through phase equilibration of IBr. Considering the extent of sea ice around the Antarctic continent, we suggest that the resulting high levels of iodine may have widespread impacts on catalytic ozone destruction and aerosol formation in the Antarctic lower troposphere.
