S. Myriokefalitakis

Simultaneous global observations of glyoxal and formaldehyde from space

[1] The first global simultaneous observations of glyoxal (CHOCHO) and formaldehyde (HCHO) columns retrieved from measurements by the Scanning Imaging Absorption Spectrometer for Atmospheric Cartography (SCIAMACHY) satellite instrument are presented and compared to model calculations. The global pattern of the distribution of CHOCHO is similar to that of HCHO. High values are observed over areas with large biogenic isoprene emissions (Central Africa, parts of South America, and Indonesia). Also regions with biomass burning and anthropogenic pollution exhibit elevated levels of CHOCHO. The ratio of the columns of CHOCHO to HCHO is generally of the order of 0.05 in regions having biogenic emissions, which is in reasonable agreement with the current understanding of the oxidation of hydrocarbons emitted by the biosphere. However and in contrast to our model, high values of both HCHO and CHOCHO are also observed over areas of the tropical oceans. This is tentatively attributed to outflow from the continents and local oceanic biogenic sources of the precursors of HCHO and CHOCHO. Citation: Wittrock, F., A. Richter, H. Oetjen, J. P. Burrows, M. Kanakidou, S. Myriokefalitakis, R. Volkamer, S. Beirle, U. Platt, and T. Wagner (2006), Simultaneous global observations of glyoxal and formaldehyde from space, Geophys. Res. Lett., 33, L16804, doi:10.1029/2006GL026310.

Global Modeling of the Oceanic Source of Organic Aerosols

The global marine organic aerosol budget is investigated by a 3-dimensional chemistry-transport model considering recently proposed parameterisations of the primary marine organic aerosol (POA) and secondary organic aerosol (SOA) formation from the oxidation of marine volatile organic compounds. MODIS and SeaWiFS satellite data of Chlorophyll-a and ECMWF solar incoming radiation, wind speed, and temperature are driving the oceanic emissions in the model. Based on the adopted parameterisations, the SOA and the submicron POA marine sources are evaluated at about 5 Tg (1.5 Tg C ) and 7 to 8 Tg (4 Tg C ), respectively. The computed marine SOA originates from the dimethylsulfide oxidation (78%), the potentially formed dialkyl amine salts (21%), and marine hydrocarbon oxidation (0.1%). Comparison of calculations with observations indicates an additional marine source of soluble organic carbon that could be partially encountered by marine POA chemical ageing.

Past, Present, and Future Atmospheric Nitrogen Deposition

Reactive nitrogen emissions into the atmosphere are increasing due to human activities, affecting nitrogen deposition to the surface and impacting the productivity of terrestrial and marine ecosystems. An atmospheric chemistry-transport model (TM4-ECPL) is here used to calculate the global distribution of total nitrogen deposition, accounting for the first time for both its inorganic and organic fractions in gaseous and particulate phases, and past and projected changes due to anthropogenic activities. The anthropogenic and biomass burning ACCMIP historical and RCP6.0 and RCP8.5 emissions scenarios are used. Accounting for organic nitrogen (ON) primary emissions, the present-day global nitrogen atmospheric source is about 60% anthropogenic, while total N deposition increases by about 20% relative to simulations without ON primary emissions. About 20-25% of total deposited N is ON. About 10% of the emitted nitrogen oxides are deposited as ON instead of inorganic nitrogen (IN) as is considered in most global models. Almost a 3-fold increase over land (2-fold over the ocean) has been calculated for soluble N deposition due to human activities from 1850 to present. The investigated projections indicate significant changes in the regional distribution of N deposition and chemical composition, with reduced compounds gaining importance relative to oxidized ones, but very small changes in the global total flux. Sensitivity simulations quantify uncertainties due to the investigated model parameterizations of IN partitioning onto aerosols and of N chemically fixed on organics to be within 10% for the total soluble N deposition and between 25-35% for the dissolved ON deposition. Larger uncertainties are associated with N emissions.

Understanding the nature of atmospheric acid processing of mineral dusts in supplying bioavailable phosphorus to the oceans

Significance Mineral dust is the most important external source of phosphorus (P), a key nutrient controlling phytoplankton productivity and carbon uptake, to the offshore ocean. The bioavailable P in dust exhibits considerable and poorly understood variability. Detailed laboratory experiments elucidate and quantify the major processes controlling P dissolution in the atmosphere. Dust exposure to acids is the main driver of P mineral transformations, and a simple direct proportionality is found between the amount of bioavailable P dissolved from the dust and acid exposure. Simulations suggest that dust acidification increases leachable P over large areas of the globe and explains much of its variability in important oceanic areas where primary productivity is limited by this nutrient (e.g., North Central Atlantic, Mediterranean). Acidification of airborne dust particles can dramatically increase the amount of bioavailable phosphorus (P) deposited on the surface ocean. Experiments were conducted to simulate atmospheric processes and determine the dissolution behavior of P compounds in dust and dust precursor soils. Acid dissolution occurs rapidly (seconds to minutes) and is controlled by the amount of H+ ions present. For H+ < 10−4 mol/g of dust, 1–10% of the total P is dissolved, largely as a result of dissolution of surface-bound forms. At H+ > 10−4 mol/g of dust, the amount of P (and calcium) released has a direct proportionality to the amount of H+ consumed until all inorganic P minerals are exhausted and the final pH remains acidic. Once dissolved, P will stay in solution due to slow precipitation kinetics. Dissolution of apatite-P (Ap-P), the major mineral phase in dust (79–96%), occurs whether calcium carbonate (calcite) is present or not, although the increase in dissolved P is greater if calcite is absent or if the particles are externally mixed. The system was modeled adequately as a simple mixture of Ap-P and calcite. P dissolves readily by acid processes in the atmosphere in contrast to iron, which dissolves more slowly and is subject to reprecipitation at cloud water pH. We show that acidification can increase bioavailable P deposition over large areas of the globe, and may explain much of the previously observed patterns of variability in leachable P in oceanic areas where primary productivity is limited by this nutrient (e.g., Mediterranean).

Ozone and carbon monoxide budgets over the Eastern Mediterranean.

The importance of the long-range transport (LRT) on O3 and CO budgets over the Eastern Mediterranean has been investigated using the state-of-the-art 3-dimensional global chemistry-transport model TM4-ECPL. A 3-D budget analysis has been performed separating the Eastern from the Western basins and the boundary layer (BL) from the free troposphere (FT). The FT of the Eastern Mediterranean is shown to be a strong receptor of polluted air masses from the Western Mediterranean, and the most important source of polluted air masses for the Eastern Mediterranean BL, with about 40% of O3 and of CO in the BL to be transported from the FT aloft. Regional anthropogenic sources are found to have relatively small impact on regional air quality in the area, contributing by about 8% and 18% to surface levels of O3 and CO, respectively. Projections using anthropogenic emissions for the year 2050 but neglecting climate change calculate a surface O3 decrease of about 11% together with a surface CO increase of roughly 10% in the Eastern Mediterranean.

Observation- and Model-Based Estimates of Particulate Dry Nitrogen Deposition to the Oceans

Anthropogenic nitrogen (N) emissions to the atmosphere have increased significantly the deposition of nitrate (NO3-) and ammonium (NH4+) to the surface waters of the open ocean, with potential impacts on marine productivity and the global carbon cycle. Global-scale understanding of the impacts of N deposition to the oceans is reliant on our ability to produce and validate models of nitrogen emission, atmospheric chemistry, transport and deposition. In this work, ~2900 observations of aerosol NO3- and NH4+ concentrations, acquired from sampling aboard ships in the period 1995 - 2012, are used to assess the performance of modelled N concentration and deposition fields over the remote ocean. Three ocean regions (the eastern tropical North Atlantic, the northern Indian Ocean and northwest Pacific) were selected, in which the density and distribution of observational data were considered sufficient to provide effective comparison to model products. All of these study regions are affected by transport and deposition of mineral dust, which alters the deposition of N, due to uptake of nitrogen oxides (NOx) on mineral surfaces. Assessment of the impacts of atmospheric N deposition on the ocean requires atmospheric chemical transport models to report deposition fluxes, however these fluxes cannot be measured over the ocean. Modelling studies such as the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP), which only report deposition flux are therefore very difficult to validate for dry deposition. Here the available observational data were averaged over a 5° × 5° grid and compared to ACCMIP dry deposition fluxes (ModDep) of oxidised N (NOy) and reduced N (NHx) and to the following parameters from the TM4-ECPL (TM4) model: ModDep for NOy, NHx and particulate NO3- and NH4+, and surface-level particulate NO3- and NH4+ concentrations. As a model ensemble, ACCMIP can be expected to be more robust than TM4, while TM4 gives access to speciated parameters (NO3- and NH4+) that are more relevant to the observed parameters and which are not available in ACCMIP. Dry deposition fluxes (CalDep) were calculated from the observed concentrations using estimates of dry deposition velocities. Model - observation ratios, weighted by grid-cell area and numbers of observations, (RA,n) were used to assess the performance of the models. Comparison in the three study regions suggests that TM4 over-estimates NO3- concentrations (RA,n = 1.4 - 2.9) and under-estimates NH4+ concentrations (RA,n = 0.5 - 0.7), with spatial distributions in the tropical Atlantic and northern Indian Ocean not being reproduced by the model. In the case of NH4+ in the Indian Ocean, this discrepancy was probably due to seasonal biases in the sampling. Similar patterns were observed in the various comparisons of CalDep to ModDep (RA,n = 0.6 - 2.6 for NO3-, 0.6 - 3.1 for NH4+). Values of RA,n for NHx CalDep - ModDep comparisons were approximately double the corresponding values for NH4+ CalDep - ModDep comparisons due to the significant fraction of gas-phase NH3 deposition incorporated in the TM4 and ACCMIP NHx model products. All of the comparisons suffered due to the scarcity of observational data and the large uncertainty in dry deposition velocities used to derive deposition fluxes from concentrations. These uncertainties have been a major limitation on estimates of the flux of material to the oceans for several decades. Recommendations are made for improvements in N deposition estimation through changes in observations, modelling and model - observation comparison procedures. Validation of modelled dry deposition requires effective comparisons to observable aerosol-phase species concentrations and this cannot be achieved if model products only report dry deposition flux over the ocean.

Simulated air quality and pollutant budgets over Europe in 2008

Major gaseous and particulate pollutant levels over Europe in 2008 have been simulated using the offline-coupled WRFCMAQ chemistry and transport modeling system. The simulations are compared with surface observations from the EMEP stations, ozone (O3) soundings, ship-borne O3 and nitrogen dioxide (NO2) observations in the western Mediterranean, tropospheric NO2 vertical column densities from the SCIAMACHY instrument, and aerosol optical depths (AOD) from the AERONET. The results show that on average, surface O3 levels are underestimated by 4 to 7% over the northern European EMEP stations while they are overestimated by 7-10% over the southern European EMEP stations and underestimated in the tropospheric column (by 10-20%). Particulate matter (PM) mass concentrations are underestimated by up to 60%, particularly in southern and eastern Europe, suggesting underestimated PM sources. Larger differences are calculated for individual aerosol components, particularly for organic and elemental carbon than for the total PM mass, indicating uncertainty in the combustion sources. Better agreement has been obtained for aerosol species over urban areas of the eastern Mediterranean, particularly for nss-SO4(2), attributed to the implementation of higher quality emission inventories for that area. Simulated AOD levels are lower than the AERONET observations by 10% on average, with average underestimations of 3% north of 40°N, attributed to the low anthropogenic emissions in the model and 22% south of 40°N, suggesting underestimated natural and resuspended dust emissions. Overall, the results reveal differences in the model performance between northern and southern Europe, suggesting significant differences in the representation of both anthropogenic and natural emissions in these regions. Budget analyses indicate that O3 and peroxyacetyl nitrate (PAN) are transported from the free troposphere (FT) to the planetary boundary layer over Europe, while other species follow the reverse path and are then advected away from the source region.

Evaluation of a Coupled Mesoscale Meteorology and Chemistry Model Over the Mediterranean

The performance of the coupled mesoscale meteorology and chemistry model WRF/CHEM to simulate the atmospheric composition over the Mediterranean is here evaluated. The model configuration applied for this study uses the gas phase chemical mechanism Mozart and a spatial resolution of 36 × 36 km, which nests in lower resolutions (12 × 12 km and 7.2 × 7.2 km). Anthropogenic surface emissions developed in the frame of the ECLIPSE EU FP7 project and biomass burning emissions from the FINN database are used. Mineral dust aerosol emissions are derived from the GOCART dust model and biogenic emissions are calculated online by the MEGAN model. The global 3-dimensional chemistry-transport model TM4-ECPL is providing the initial and boundaries chemical conditions for the coarse resolution mesoscale model. The results show that the mesoscale model overestimates O3 surface levels at most stations by up to about 70 % and underestimates CO surface levels by up to about 25 %. Strong correlations between simulations and observations are computed for 60 % of the studied O3 stations and 20 % of the studied CO stations. No significant change in the model performance as a function of the studied model resolutions was found.

The Contribution of Bioaerosols to the Organic Carbon Budget of the Atmosphere

Primary Biological Aerosol Particles (PBAPs), commonly known also as bioaerosols, are airborne particles that include mainly bacteria, fungi spores, pollen, viruses, microorganisms or even leaf debris and usually dominate the aerosol mass over remote forested regions. The atmospheric cycle of PBAPs is here parameterized in a state-of-the-art global 3-D chemistry-transport model by taking into account their primary emissions as well as their chemical aging during the long-range transport in the atmosphere. Different ecosystems are used to parameterize the respective flux rates of PBAPs considering bacteria, fungal spores and pollen, and using meteorological parameters in order to account for fluxes seasonal variation. Bioaerosols are assumed to be emitted as 50 % hydrophilic particles but they can be transferred to the soluble mode via atmospheric oxidation, changing thus their physical properties and their atmospheric lifetime. The global annual flux of PBAPs to the atmosphere calculated by the model equals about 123 Tg yr−1 (47.5 Tg-C yr−1) and the atmospheric burden is calculated to equal about 791 Gg. These calculated emissions largely depend on the assumed size distribution and is comparable to the amount of primary particulate organic carbon injected into the atmosphere by anthropogenic emissions.

Study of the Impact of an Intense Biomass Burning Event on the Air Quality in the Eastern Mediterranean

Aim of this work is to study the impact of the intense forest fires that tookplace in Greece at the end of summer 2007 on the air quality in the Eastern Mediterranean. For this reason the meteorological model MM5 and the photochemical model CAMx are applied over the study area with 10 km spatial resolution. CAMx model is implemented for two emission scenarios; with and without biomass burning emissions. High spatial resolution wildfire emission data are used that are based on the Global Fire Emissions Database (GFED3). The CAMx chemical boundary conditions are taken from the TM4 global model. The nonradiative impact on the composition of the atmosphere and on environmental indices (e.g. Aggregate Risk Index) is quantified in regional scale. The impact of the atmospheric processes on the air pollution levels due to the biomass burning event is also studied giving more emphasis on the boundary layer. The intense biomass burning event in the Eastern Mediterranean at the end of August 2007 results in an enhancement of the CO, NOx and PM2.5 concentrations over almost all the study area, which can range from several times to two order of magnitude over the fire hot spots. The increases in O3 levels are less pronounced and are found mainly downwind the burnt areas. On the 25th August 2007, when fire counts in the study area are maximum, in the daytime boundary layer, the inclusion of biomass burning emissions results in a change of the chemical regime from O3 destruction to O3 production.