Showing papers in "Atmospheric Chemistry and Physics in 2010"

Global fire emissions and the contribution of deforestation, savanna, forest, agricultural, and peat fires (1997-2009)

Abstract: . New burned area datasets and top-down constraints from atmospheric concentration measurements of pyrogenic gases have decreased the large uncertainty in fire emissions estimates. However, significant gaps remain in our understanding of the contribution of deforestation, savanna, forest, agricultural waste, and peat fires to total global fire emissions. Here we used a revised version of the Carnegie-Ames-Stanford-Approach (CASA) biogeochemical model and improved satellite-derived estimates of area burned, fire activity, and plant productivity to calculate fire emissions for the 1997–2009 period on a 0.5° spatial resolution with a monthly time step. For November 2000 onwards, estimates were based on burned area, active fire detections, and plant productivity from the MODerate resolution Imaging Spectroradiometer (MODIS) sensor. For the partitioning we focused on the MODIS era. We used maps of burned area derived from the Tropical Rainfall Measuring Mission (TRMM) Visible and Infrared Scanner (VIRS) and Along-Track Scanning Radiometer (ATSR) active fire data prior to MODIS (1997–2000) and estimates of plant productivity derived from Advanced Very High Resolution Radiometer (AVHRR) observations during the same period. Average global fire carbon emissions according to this version 3 of the Global Fire Emissions Database (GFED3) were 2.0 Pg C year−1 with significant interannual variability during 1997–2001 (2.8 Pg C year−1 in 1998 and 1.6 Pg C year−1 in 2001). Globally, emissions during 2002–2007 were relatively constant (around 2.1 Pg C year−1) before declining in 2008 (1.7 Pg C year−1) and 2009 (1.5 Pg C year−1) partly due to lower deforestation fire emissions in South America and tropical Asia. On a regional basis, emissions were highly variable during 2002–2007 (e.g., boreal Asia, South America, and Indonesia), but these regional differences canceled out at a global level. During the MODIS era (2001–2009), most carbon emissions were from fires in grasslands and savannas (44%) with smaller contributions from tropical deforestation and degradation fires (20%), woodland fires (mostly confined to the tropics, 16%), forest fires (mostly in the extratropics, 15%), agricultural waste burning (3%), and tropical peat fires (3%). The contribution from agricultural waste fires was likely a lower bound because our approach for measuring burned area could not detect all of these relatively small fires. Total carbon emissions were on average 13% lower than in our previous (GFED2) work. For reduced trace gases such as CO and CH4, deforestation, degradation, and peat fires were more important contributors because of higher emissions of reduced trace gases per unit carbon combusted compared to savanna fires. Carbon emissions from tropical deforestation, degradation, and peatland fires were on average 0.5 Pg C year−1. The carbon emissions from these fires may not be balanced by regrowth following fire. Our results provide the first global assessment of the contribution of different sources to total global fire emissions for the past decade, and supply the community with an improved 13-year fire emissions time series.

Historical (1850–2000) gridded anthropogenic and biomass burning emissions of reactive gases and aerosols: methodology and application

Abstract: We present and discuss a new dataset of gridded emissions covering the historical period (1850–2000) in decadal increments at a horizontal resolution of 0.5° in latitude and longitude. The primary purpose of this inventory is to provide consistent gridded emissions of reactive gases and aerosols for use in chemistry model simulations needed by climate models for the Climate Model Intercomparison Program #5 (CMIP5) in support of the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (AR5). Our best estimate for the year 2000 inventory represents a combination of existing regional and global inventories to capture the best information available at this point; 40 regions and 12 sectors are used to combine the various sources. The historical reconstruction of each emitted compound, for each region and sector, is then forced to agree with our 2000 estimate, ensuring continuity between past and 2000 emissions. Simulations from two chemistry-climate models is used to test the ability of the emission dataset described here to capture long-term changes in atmospheric ozone, carbon monoxide and aerosol distributions. The simulated long-term change in the Northern mid-latitudes surface and mid-troposphere ozone is not quite as rapid as observed. However, stations outside this latitude band show much better agreement in both present-day and long-term trend. The model simulations indicate that the concentration of carbon monoxide is underestimated at the Mace Head station; however, the long-term trend over the limited observational period seems to be reasonably well captured. The simulated sulfate and black carbon deposition over Greenland is in very good agreement with the ice-core observations spanning the simulation period. Finally, aerosol optical depth and additional aerosol diagnostics are shown to be in good agreement with previously published estimates and observations.

Global mercury emissions to the atmosphere from anthropogenic and natural sources

Abstract: . This paper provides an up-to-date assessment of global mercury emissions from anthropogenic and natural sources. On an annual basis, natural sources account for 5207 Mg of mercury released to the global atmosphere, including the contribution from re-emission processes, which are emissions of previously deposited mercury originating from anthropogenic and natural sources, and primary emissions from natural reservoirs. Anthropogenic sources, which include a large number of industrial point sources, are estimated to account for 2320 Mg of mercury emitted annually. The major contributions are from fossil-fuel fired power plants (810 Mg yr−1), artisanal small scale gold mining (400 Mg yr−1), non-ferrous metals manufacturing (310 Mg yr−1), cement production (236 Mg yr−1), waste disposal (187 Mg yr−1) and caustic soda production (163 Mg yr−1). Therefore, our current estimate of global mercury emissions suggests that the overall contribution from natural sources (primary emissions + re-emissions) and anthropogenic sources is nearly 7527 Mg per year, the uncertainty associated with these estimates are related to the typology of emission sources and source regions.

Global evaluation of the Collection 5 MODIS dark-target aerosol products over land

Abstract: . NASA's MODIS sensors have been observing the Earth from polar orbit, from Terra since early 2000 and from Aqua since mid 2002. We have applied a consistent retrieval and processing algorithm to both sensors to derive the Collection 5 (C005) dark-target aerosol products over land. Here, we validate the MODIS along-orbit Level 2 products by comparing to quality assured Level 2 AERONET sunphotometer measurements at over 300 sites. From 85 463 collocations, representing mutually cloud-free conditions, we find that >66% (one standard deviation) of MODIS-retrieved aerosol optical depth (AOD) values compare to AERONET-observed values within an expected error (EE) envelope of ±(0.05 + 15%), with high correlation (R = 0.9). Thus, the MODIS AOD product is validated and quantitative. However, even though we can define EEs for MODIS-reported Angstrom exponent and fine AOD over land, these products do not have similar physical validity. Although validated globally, MODIS-retrieved AOD does not fall within the EE envelope everywhere. We characterize some of the residual biases that are related to specific aerosol conditions, observation geometry, and/or surface properties, and relate them to situations where particular MODIS algorithm assumptions are violated. Both Terra's and Aqua's–retrieved AOD are similarly comparable to AERONET, however, Terra's global AOD bias changes with time, overestimating (by ~0.005) before 2004, and underestimating by similar magnitude after. This suggests how small calibration uncertainties of

Organic aerosol components observed in Northern Hemispheric datasets from Aerosol Mass Spectrometry

Abstract: . In this study we compile and present results from the factor analysis of 43 Aerosol Mass Spectrometer (AMS) datasets (27 of the datasets are reanalyzed in this work). The components from all sites, when taken together, provide a holistic overview of Northern Hemisphere organic aerosol (OA) and its evolution in the atmosphere. At most sites, the OA can be separated into oxygenated OA (OOA), hydrocarbon-like OA (HOA), and sometimes other components such as biomass burning OA (BBOA). We focus on the OOA components in this work. In many analyses, the OOA can be further deconvolved into low-volatility OOA (LV-OOA) and semi-volatile OOA (SV-OOA). Differences in the mass spectra of these components are characterized in terms of the two main ions m/z 44 (CO2+) and m/z 43 (mostly C2H3O+), which are used to develop a new mass spectral diagnostic for following the aging of OA components in the atmosphere. The LV-OOA component spectra have higher f44 (ratio of m/z 44 to total signal in the component mass spectrum) and lower f43 (ratio of m/z 43 to total signal in the component mass spectrum) than SV-OOA. A wide range of f44 and O:C ratios are observed for both LV-OOA (0.17±0.04, 0.73±0.14) and SV-OOA (0.07±0.04, 0.35±0.14) components, reflecting the fact that there is a continuum of OOA properties in ambient aerosol. The OOA components (OOA, LV-OOA, and SV-OOA) from all sites cluster within a well-defined triangular region in the f44 vs. f43 space, which can be used as a standardized means for comparing and characterizing any OOA components (laboratory or ambient) observed with the AMS. Examination of the OOA components in this triangular space indicates that OOA component spectra become increasingly similar to each other and to fulvic acid and HULIS sample spectra as f44 (a surrogate for O:C and an indicator of photochemical aging) increases. This indicates that ambient OA converges towards highly aged LV-OOA with atmospheric oxidation. The common features of the transformation between SV-OOA and LV-OOA at multiple sites potentially enable a simplified description of the oxidation of OA in the atmosphere. Comparison of laboratory SOA data with ambient OOA indicates that laboratory SOA are more similar to SV-OOA and rarely become as oxidized as ambient LV-OOA, likely due to the higher loadings employed in the experiments and/or limited oxidant exposure in most chamber experiments.

Light absorption by organic carbon from wood combustion

Abstract: . Carbonaceous aerosols affect the radiative balance of the Earth by absorbing and scattering light. While black carbon (BC) is highly absorbing, some organic carbon (OC) also has significant absorption, especially at near-ultraviolet and blue wavelengths. To the extent that OC absorbs visible light, it may be a non-negligible contributor to positive direct aerosol radiative forcing. Quantification of that absorption is necessary so that radiative-transfer models can evaluate the net radiative effect of OC. In this work, we examine absorption by primary OC emitted from solid fuel pyrolysis. We provide absorption spectra of this material, which can be related to the imaginary refractive index. This material has polar character but is not fully water-soluble: more than 92% was extractable by methanol or acetone, compared with 73% for water and 52% for hexane. Water-soluble OC contributes to light absorption at both ultraviolet and visible wavelengths. However, a larger portion of the absorption comes from OC that is extractable only by methanol. Absorption spectra of water-soluble OC are similar to literature reports. We compare spectra for material generated with different wood type, wood size and pyrolysis temperature. Higher wood temperature is the main factor creating OC with higher absorption; changing wood temperature from a devolatilizing state of 210 °C to a near-flaming state of 360 °C causes about a factor of four increase in mass-normalized absorption at visible wavelengths. A clear-sky radiative transfer model suggests that, despite the absorption, both high-temperature and low-temperature OC result in negative top-of-atmosphere radiative forcing over a surface with an albedo of 0.19 and positive radiative forcing over bright surfaces. Unless absorption by real ambient aerosol is higher than that measured here, it probably affects global average clear-sky forcing very little, but could be important in energy balances over bright surfaces.

Absorption Angstrom Exponent in AERONET and related data as an indicator of aerosol composition

Abstract: . Recent results from diverse air, ground, and laboratory studies using both radiometric and in situ techniques show that the fractions of black carbon, organic matter, and mineral dust in atmospheric aerosols determine the wavelength dependence of absorption (often expressed as Absorption Angstrom Exponent, or AAE). Taken together, these results hold promise of improving information on aerosol composition from remote measurements. The main purpose of this paper is to show that AAE values for an Aerosol Robotic Network (AERONET) set of retrievals from Sun-sky measurements describing full aerosol vertical columns are also strongly correlated with aerosol composition or type. In particular, we find AAE values near 1 (the theoretical value for black carbon) for AERONET-measured aerosol columns dominated by urban-industrial aerosol, larger AAE values for biomass burning aerosols, and the largest AAE values for Sahara dust aerosols. These AERONET results are consistent with results from other, very different, techniques, including solar flux-aerosol optical depth (AOD) analyses and airborne in situ analyses examined in this paper, as well as many other previous results. Ambiguities in aerosol composition or mixtures thereof, resulting from intermediate AAE values, can be reduced via cluster analyses that supplement AAE with other variables, for example Extinction Angstrom Exponent (EAE), which is an indicator of particle size. Together with previous results, these results strengthen prospects for determining aerosol composition from space, for example using the Glory Aerosol Polarimetry Sensor (APS), which seeks to provide retrievals of multiwavelength single-scattering albedo (SSA) and aerosol optical depth (and therefore aerosol absorption optical depth (AAOD) and AAE), as well as shape and other aerosol properties. Multidimensional cluster analyses promise additional information content, for example by using the Ozone Monitoring Instrument (OMI) to add AAOD in the near ultraviolet and CALIPSO aerosol layer heights to reduce height-absorption ambiguity.

Sulfur dioxide emissions in China and sulfur trends in East Asia since 2000

Abstract: . With the rapid development of the economy, the sulfur dioxide (SO2) emission from China since 2000 is of increasing concern. In this study, we estimate the annual SO2 emission in China after 2000 using a technology-based methodology specifically for China. From 2000 to 2006, total SO2 emission in China increased by 53%, from 21.7 Tg to 33.2 Tg, at an annual growth rate of 7.3%. Emissions from power plants are the main sources of SO2 in China and they increased from 10.6 Tg to 18.6 Tg in the same period. Geographically, emission from north China increased by 85%, whereas that from the south increased by only 28%. The emission growth rate slowed around 2005, and emissions began to decrease after 2006 mainly due to the wide application of flue-gas desulfurization (FGD) devices in power plants in response to a new policy of China's government. This paper shows that the trend of estimated SO2 emission in China is consistent with the trends of SO2 concentration and acid rain pH and frequency in China, as well as with the increasing trends of background SO2 and sulfate concentration in East Asia. A longitudinal gradient in the percentage change of urban SO2 concentration in Japan is found during 2000–2007, indicating that the decrease of urban SO2 is lower in areas close to the Asian continent. This implies that the transport of increasing SO2 from the Asian continent partially counteracts the local reduction of SO2 emission downwind. The aerosol optical depth (AOD) products of Moderate Resolution Imaging Spectroradiometer (MODIS) are found to be highly correlated with the surface solar radiation (SSR) measurements in East Asia. Using MODIS AOD data as a surrogate of SSR, we found that China and East Asia excluding Japan underwent a continuous dimming after 2000, which is in line with the dramatic increase in SO2 emission in East Asia. The trends of AOD from both satellite retrievals and model over East Asia are also consistent with the trend of SO2 emission in China, especially during the second half of the year, when sulfur contributes the largest fraction of AOD. The arrested growth in SO2 emissions since 2006 is also reflected in the decreasing trends of SO2 and SO42− concentrations, acid rain pH values and frequencies, and AOD over East Asia.

A review of natural aerosol interactions and feedbacks within the Earth system

Abstract: . The natural environment is a major source of atmospheric aerosols, including dust, secondary organic material from terrestrial biogenic emissions, carbonaceous particles from wildfires, and sulphate from marine phytoplankton dimethyl sulphide emissions. These aerosols also have a significant effect on many components of the Earth system such as the atmospheric radiative balance and photosynthetically available radiation entering the biosphere, the supply of nutrients to the ocean, and the albedo of snow and ice. The physical and biological systems that produce these aerosols can be highly susceptible to modification due to climate change so there is the potential for important climate feedbacks. We review the impact of these natural systems on atmospheric aerosol based on observations and models, including the potential for long term changes in emissions and the feedbacks on climate. The number of drivers of change is very large and the various systems are strongly coupled. There have therefore been very few studies that integrate the various effects to estimate climate feedback factors. Nevertheless, available observations and model studies suggest that the regional radiative perturbations are potentially several Watts per square metre due to changes in these natural aerosol emissions in a future climate. Taking into account only the direct radiative effect of changes in the atmospheric burden of natural aerosols, and neglecting potentially large effects on other parts of the Earth system, a global mean radiative perturbation approaching 1 W m−2 is possible by the end of the century. The level of scientific understanding of the climate drivers, interactions and impacts is very low.

Black carbon semi-direct effects on cloud cover: review and synthesis

Abstract: . Absorbing aerosols (AAs) such as black carbon (BC) or dust absorb incoming solar radiation, perturb the temperature structure of the atmosphere, and influence cloud cover. Previous studies have described conditions under which AAs either increase or decrease cloud cover. The effect depends on several factors, including the altitude of the AA relative to the cloud and the cloud type. We attempt to categorize the effects into several likely regimes. Cloud cover is decreased if the AAs are embedded in the cloud layer. AAs below cloud may enhance convection and cloud cover. AAs above cloud top stabilize the underlying layer and tend to enhance stratocumulus clouds but may reduce cumulus clouds. AAs can also promote cloud cover in convergent regions as they enhance deep convection and low level convergence as it draws in moisture from ocean to land regions. Most global model studies indicate a regional variation in the cloud response but generally increased cloud cover over oceans and some land regions, with net increased low-level and/or reduced upper level cloud cover. The result is a net negative semi-direct effect feedback from the cloud response to AAs. In some of these climate model studies, the cooling effect of BC due to cloud changes is strong enough to essentially cancel the warming direct effects.

Aqueous chemistry and its role in secondary organic aerosol (SOA) formation

Abstract: . There is a growing understanding that secondary organic aerosol (SOA) can form through reactions in atmospheric waters (i.e., clouds, fogs, and aerosol water). In clouds and wet aerosols, water-soluble organic products of gas-phase photochemistry dissolve into the aqueous phase where they can react further (e.g., with OH radicals) to form low volatility products that are largely retained in the particle phase. Organic acids, oligomers and other products form via radical and non-radical reactions, including hemiacetal formation during droplet evaporation, acid/base catalysis, and reaction of organics with other constituents (e.g., NH4+). This paper provides an overview of SOA formation through aqueous chemistry, including atmospheric evidence for this process and a review of radical and non-radical chemistry, using glyoxal as a model precursor. Previously unreported analyses and new kinetic modeling are reported herein to support the discussion of radical chemistry. Results suggest that reactions with OH radicals tend to be faster and form more SOA than non-radical reactions. In clouds these reactions yield organic acids, whereas in wet aerosols they yield large multifunctional humic-like substances formed via radical-radical reactions and their O/C ratios are near 1.

Water-Soluble Organic Aerosol material and the light-absorption characteristics of aqueous extracts measured over the Southeastern United States

Abstract: . Light absorption of fine particle (PM2.5) aqueous extracts between wavelengths of 200 and 800 nm were investigated from two data sets: 24-h Federal Reference Method (FRM) filter extracts from 15 Southeastern US monitoring sites over the year of 2007 (900 filters), and online measurements from a Particle-Into-Liquid Sampler deployed from July to mid-August 2009 in Atlanta, Georgia. Three main sources of soluble chromophores were identified: biomass burning, mobile source emissions, and compounds linked to secondary organic aerosol (SOA) formation. Absorption spectra of aerosol solutions from filter extracts were similar for different sources. Angstrom exponents were ~7±1 for biomass burning and non-biomass burning-impacted 24-h filter samples (delineated by a levoglucosan concentration of 50 ng m−3) at both rural and urban sites. The absorption coefficient from measurements averaged between wavelength 360 and 370 nm (Abs365, in units m−1) was used as a measure of overall brown carbon light absorption. Biomass-burning-impacted samples were highest during winter months and Abs365 was correlated with levoglucosan at all sites. During periods of little biomass burning in summer, light absorbing compounds were still ubiquitous and correlated with fine particle Water-Soluble Organic Carbon (WSOC), but comprised a much smaller fraction of the WSOC, where Abs365/WSOC (i.e., mass absorption efficiency) was typically ~3 times higher in biomass burning-impacted samples. Factor analysis attributed 50% of the yearly average Abs365 to biomass burning sources. Brown carbon from primary urban emissions (mobile sources) was also observed and accounted for ~10% of the regional yearly average Abs365. Summertime diurnal profiles of Abs365 and WSOC showed that morning to midday increases in WSOC from photochemical production were associated with a decrease in Abs365/WSOC. After noon, this ratio substantially increased, indicating that either some fraction of the non-light absorbing fresh SOA was rapidly (within hours) converted to chromophores heterogeneously, or that SOA from gas-particle partitioning later in the day was more light-absorbing. Factor analysis on the 24-h integrated filter data associated ~20 to 30% of Abs365 over 2007 with a secondary source that was highest in summer and also the main source for oxalate, suggesting that aqueous phase reactions may account for the light-absorbing fraction of WSOC observed throughout the Southeastern US in summer.

Atmospheric pollutant outflow from southern Asia: a review

Abstract: . Southern Asia, extending from Pakistan and Afghanistan to Indonesia and Papua New Guinea, is one of the most heavily populated regions of the world. Biofuel and biomass burning play a disproportionately large role in the emissions of most key pollutant gases and aerosols there, in contrast to much of the rest of the Northern Hemisphere, where fossil fuel burning and industrial processes tend to dominate. This results in polluted air masses which are enriched in carbon-containing aerosols, carbon monoxide, and hydrocarbons. The outflow and long-distance transport of these polluted air masses is characterized by three distinct seasonal circulation patterns: the winter monsoon, the summer monsoon, and the monsoon transition periods. During winter, the near-surface flow is mostly northeasterly, and the regional pollution forms a thick haze layer in the lower troposphere which spreads out over millions of square km between southern Asia and the Intertropical Convergence Zone (ITCZ), located several degrees south of the equator over the Indian Ocean during this period. During summer, the heavy monsoon rains effectively remove soluble gases and aerosols. Less soluble species, on the other hand, are lifted to the upper troposphere in deep convective clouds, and are then transported away from the region by strong upper tropospheric winds, particularly towards northern Africa and the Mediterranean in the tropical easterly jet. Part of the pollution can reach the tropical tropopause layer, the gateway to the stratosphere. During the monsoon transition periods, the flow across the Indian Ocean is primarily zonal, and strong pollution plumes originating from both southeastern Asia and from Africa spread across the central Indian Ocean. This paper provides a review of the current state of knowledge based on the many observational and modeling studies over the last decades that have examined the southern Asian atmospheric pollutant outflow and its large scale effects. An outlook is provided as a guideline for future research, pointing out particularly critical issues such as: resolving discrepancies between top down and bottom up emissions estimates; assessing the processing and aging of the pollutant outflow; developing a better understanding of the observed elevated pollutant layers and their relationship to local sea breeze and large scale monsoon circulations; and determining the impacts of the pollutant outflow on the Asian monsoon meteorology and the regional hydrological cycle, in particular the mountain cryospheric reservoirs and the fresh water supply, which in turn directly impact the lives of over a billion inhabitants of southern Asia.

Global atmospheric model for mercury including oxidation by bromine atoms

Abstract: . Global models of atmospheric mercury generally assume that gas-phase OH and ozone are the main oxidants converting Hg0 to HgII and thus driving mercury deposition to ecosystems. However, thermodynamic considerations argue against the importance of these reactions. We demonstrate here the viability of atomic bromine (Br) as an alternative Hg0 oxidant. We conduct a global 3-D simulation with the GEOS-Chem model assuming gas-phase Br to be the sole Hg0 oxidant (Hg + Br model) and compare to the previous version of the model with OH and ozone as the sole oxidants (Hg + OH/O3 model). We specify global 3-D Br concentration fields based on our best understanding of tropospheric and stratospheric Br chemistry. In both the Hg + Br and Hg + OH/O3 models, we add an aqueous photochemical reduction of HgII in cloud to impose a tropospheric lifetime for mercury of 6.5 months against deposition, as needed to reconcile observed total gaseous mercury (TGM) concentrations with current estimates of anthropogenic emissions. This added reduction would not be necessary in the Hg + Br model if we adjusted the Br oxidation kinetics downward within their range of uncertainty. We find that the Hg + Br and Hg + OH/O3 models are equally capable of reproducing the spatial distribution of TGM and its seasonal cycle at northern mid-latitudes. The Hg + Br model shows a steeper decline of TGM concentrations from the tropics to southern mid-latitudes. Only the Hg + Br model can reproduce the springtime depletion and summer rebound of TGM observed at polar sites; the snowpack component of GEOS-Chem suggests that 40% of HgII deposited to snow in the Arctic is transferred to the ocean and land reservoirs, amounting to a net deposition flux to the Arctic of 60 Mg a−1. Summertime events of depleted Hg0 at Antarctic sites due to subsidence are much better simulated by the Hg + Br model. Model comparisons to observed wet deposition fluxes of mercury in the US and Europe show general consistency. However the Hg + Br model does not capture the summer maximum over the southeast US because of low subtropical Br concentrations while the Hg + OH/O3 model does. Vertical profiles measured from aircraft show a decline of Hg0 above the tropopause that can be captured by both the Hg + Br and Hg + OH/O3 models, except in Arctic spring where the observed decline is much steeper than simulated by either model; we speculate that oxidation by Cl species might be responsible. The Hg + Br and Hg + OH/O3 models yield similar global budgets for the cycling of mercury between the atmosphere and surface reservoirs, but the Hg + Br model results in a much larger fraction of mercury deposited to the Southern Hemisphere oceans.

Brown carbon in tar balls from smoldering biomass combustion

Abstract: . We report the direct observation of laboratory production of spherical, carbonaceous particles – "tar balls" – from smoldering combustion of two commonly occurring dry mid-latitude fuels. Real-time measurements of spectrally varying absorption Angstrom coefficients (AAC) indicate that a class of light absorbing organic carbon (OC) with wavelength dependent imaginary part of its refractive index – optically defined as "brown carbon" – is an important component of tar balls. The spectrum of the imaginary parts of their complex refractive indices can be described with a Lorentzian-like model with an effective resonance wavelength in the ultraviolet (UV) spectral region. Sensitivity calculations for aerosols containing traditional OC (no absorption at visible and UV wavelengths) and brown carbon suggest that accounting for near-UV absorption by brown carbon leads to an increase in aerosol radiative forcing efficiency and increased light absorption. Since particles from smoldering combustion account for nearly three-fourths of the total carbonaceous aerosol mass emitted globally, inclusion of the optical properties of tar balls into radiative forcing models has significance for the Earth's radiation budget, optical remote sensing, and understanding of anomalous UV absorption in the troposphere.

Impact of brown and clear carbon on light absorption enhancement, single scatter albedo and absorption wavelength dependence of black carbon

Abstract: . The presence of clear coatings on atmospheric black carbon (BC) particles is known to enhance the magnitude of light absorption by the BC cores. Based on calculations using core/shell Mie theory, we demonstrate that the enhancement of light absorption (EAbs) by atmospheric black carbon (BC) when it is coated in mildly absorbing material (CBrown) is reduced relative to the enhancement induced by non-absorbing coatings (CClear). This reduction, sensitive to both the CBrown coating thickness and imaginary refractive index (RI), can be up to 50% for 400 nm radiation and 25% averaged across the visible radiation spectrum for reasonable core/shell diameters. The enhanced direct radiative forcing possible due to the enhancement effect of CClear is therefore reduced if the coating is absorbing. Additionally, the need to explicitly treat BC as an internal, as opposed to external, mixture with CBrown is shown to be important to the calculated single scatter albedo only when models treat BC as large spherical cores (>50 nm). For smaller BC cores (or fractal agglomerates) consideration of the BC and CBrown as an external mixture leads to relatively small errors in the particle single scatter albedo of 1 indicates absorption by a non-BC aerosol. Here, it is shown that BC cores coated in CClear can reasonably have an AAE of up to 1.6, a result that complicates the attribution of observed light absorption to CBrown within ambient particles. However, an AAE 1.6. Comparison of these model results to various ambient AAE measurements demonstrates that large-scale attribution of CBrown is a challenging task using current in-situ measurement methods. We suggest that coincident measurements of particle core and shell sizes along with the AAE may be necessary to distinguish absorbing and non-absorbing OC.

Light-absorbing impurities in Arctic snow

Abstract: . Absorption of radiation by ice is extremely weak at visible and near-ultraviolet wavelengths, so small amounts of light-absorbing impurities in snow can dominate the absorption of solar radiation at these wavelengths, reducing the albedo relative to that of pure snow, contributing to the surface energy budget and leading to earlier snowmelt. In this study Arctic snow is surveyed for its content of light-absorbing impurities, expanding and updating the 1983–1984 survey of Clarke and Noone. Samples were collected in Alaska, Canada, Greenland, Svalbard, Norway, Russia, and the Arctic Ocean during 1998 and 2005–2009, on tundra, glaciers, ice caps, sea ice, frozen lakes, and in boreal forests. Snow was collected mostly in spring, when the entire winter snowpack is accessible for sampling. Sampling was carried out in summer on the Greenland Ice Sheet and on the Arctic Ocean, of melting glacier snow and sea ice as well as cold snow. About 1200 snow samples have been analyzed for this study. The snow is melted and filtered; the filters are analyzed in a specially designed spectrophotometer system to infer the concentration of black carbon (BC), the fraction of absorption due to non-BC light-absorbing constituents and the absorption Angstrom exponent of all particles. This is done using BC calibration standards having a mass absorption efficiency of 6.0 m2 g−1 at 550 nm and by making an assumption that the absorption Angstrom exponent for BC is 1.0 and for non-BC light-absorbing aerosol is 5.0. The reduction of snow albedo is primarily due to BC, but other impurities, principally brown (organic) carbon, are typically responsible for ~40% of the visible and ultraviolet absorption. The meltwater from selected snow samples was saved for chemical analysis to identify sources of the impurities. Median BC amounts in surface snow are as follows (nanograms of carbon per gram of snow): Greenland 3, Arctic Ocean snow 7, melting sea ice 8, Arctic Canada 8, subarctic Canada 14, Svalbard 13, Northern Norway 21, western Arctic Russia 27, northeastern Siberia 34. Concentrations are more variable in the European Arctic than in Arctic Canada or the Arctic Ocean, probably because of the proximity to BC sources. Individual samples of falling snow were collected on Svalbard, documenting the springtime decline of BC from March through May. Absorption Angstrom exponents are 1.5–1.7 in Norway, Svalbard, and western Russia, 2.1–2.3 elsewhere in the Arctic, and 2.5 in Greenland. Correspondingly, the estimated contribution to absorption by non-BC constituents in these regions is ~25%, 40%, and 50% respectively. It has been hypothesized that when the snow surface layer melts some of the BC is left at the top of the snowpack rather than being carried away in meltwater. This process was observed in a few locations and would cause a positive feedback on snowmelt. The BC content of the Arctic atmosphere has declined markedly since 1989, according to the continuous measurements of near-surface air at Alert (Canada), Barrow (Alaska), and Ny-Alesund (Svalbard). Correspondingly, the new BC concentrations for Arctic snow are somewhat lower than those reported by Clarke and Noone for 1983–1984, but because of methodological differences it is not clear that the differences are significant. Nevertheless, the BC content of Arctic snow appears to be no higher now than in 1984, so it is doubtful that BC in Arctic snow has contributed to the rapid decline of Arctic sea ice in recent years.

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume V – heterogeneous reactions on solid substrates

Abstract: . This article, the fifth in the ACP journal series, presents data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the heterogeneous processes on surfaces of solid particles present in the atmosphere, for which uptake coefficients and adsorption parameters have been presented on the IUPAC website in 2010. The article consists of an introduction and guide to the evaluation, giving a unifying framework for parameterisation of atmospheric heterogeneous processes. We provide summary sheets containing the recommended uptake parameters for the evaluated processes. Four substantial appendices contain detailed data sheets for each process considered for ice, mineral dust, sulfuric acid hydrate and nitric acid hydrate surfaces, which provide information upon which the recommendations are made.

Observed 20th century desert dust variability: impact on climate and biogeochemistry

Abstract: Desert dust perturbs climate by directly and in- directly interacting with incoming solar and outgoing long wave radiation, thereby changing precipitation and tempera- ture, in addition to modifying ocean and land biogeochem- istry. While we know that desert dust is sensitive to pertur- bations in climate and human land use, previous studies have been unable to determine whether humans were increasing or decreasing desert dust in the global average. Here we present observational estimates of desert dust based on pa- leodata proxies showing a doubling of desert dust during the 20th century over much, but not all the globe. Large uncertainties remain in estimates of desert dust variability over 20th century due to limited data. Using these ob- servational estimates of desert dust change in combination with ocean, atmosphere and land models, we calculate the net radiative effect of these observed changes (top of at- mosphere) over the 20th century to be 0.14± 0.11 W/m 2 (1990-1999 vs. 1905-1914). The estimated radiative change

The Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission: design, execution, and first results

Abstract: . The NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was conducted in two 3-week deployments based in Alaska (April 2008) and western Canada (June–July 2008). Its goal was to better understand the factors driving current changes in Arctic atmospheric composition and climate, including (1) influx of mid-latitude pollution, (2) boreal forest fires, (3) aerosol radiative forcing, and (4) chemical processes. The June–July deployment was preceded by one week of flights over California (ARCTAS-CARB) focused on (1) improving state emission inventories for greenhouse gases and aerosols, (2) providing observations to test and improve models of ozone and aerosol pollution. ARCTAS involved three aircraft: a DC-8 with a detailed chemical payload, a P-3 with an extensive aerosol and radiometric payload, and a B-200 with aerosol remote sensing instrumentation. The aircraft data augmented satellite observations of Arctic atmospheric composition, in particular from the NASA A-Train. The spring phase (ARCTAS-A) revealed pervasive Asian pollution throughout the Arctic as well as significant European pollution below 2 km. Unusually large Siberian fires in April 2008 caused high concentrations of carbonaceous aerosols and also affected ozone. Satellite observations of BrO column hotspots were found not to be related to Arctic boundary layer events but instead to tropopause depressions, suggesting the presence of elevated inorganic bromine (5–10 pptv) in the lower stratosphere. Fresh fire plumes from Canada and California sampled during the summer phase (ARCTAS-B) indicated low NOx emission factors from the fires, rapid conversion of NOx to PAN, no significant secondary aerosol production, and no significant ozone enhancements except when mixed with urban pollution.

Mercury emission and speciation of coal-fired power plants in China

Abstract: . Comprehensive field measurements are needed to understand the mercury emissions from Chinese power plants and to improve the accuracy of emission inventories. Characterization of mercury emissions and their behavior were measured in six typical coal-fired power plants in China. During the tests, the flue gas was sampled simultaneously at inlet and outlet of Selective Catalytic Reduction (SCR), electrostatic precipitators (ESP), and flue gas desulfurization (FGD) using the Ontario Hydro Method (OHM). The pulverized coal, bottom ash, fly ash and gypsum were also sampled in the field. Mercury concentrations in coal burned in the measured power plants ranged from 17 to 385 μg/kg. The mercury mass balances for the six power plants varied from 87 to 116% of the input coal mercury for the whole system. The total mercury concentrations in the flue gas from boilers were at the range of 1.92–27.15 μg/m3, which were significantly related to the mercury contents in burned coal. The mercury speciation in flue gas right after the boiler is influenced by the contents of halogen, mercury, and ash in the burned coal. The average mercury removal efficiencies of ESP, ESP plus wet FGD, and ESP plus dry FGD-FF systems were 24%, 73% and 66%, respectively, which were similar to the average removal efficiencies of pollution control device systems in other countries such as US, Japan and South Korea. The SCR system oxidized 16% elemental mercury and reduced about 32% of total mercury. Elemental mercury, accounting for 66–94% of total mercury, was the dominant species emitted to the atmosphere. The mercury emission factor was also calculated for each power plant.

An overview of current issues in the uptake of atmospheric trace gases by aerosols and clouds

Abstract: . A workshop was held in the framework of the ACCENT (Atmospheric Composition Change – a European Network) Joint Research Programme on "Aerosols" and the Programme on "Access to Laboratory Data". The aim of the workshop was to hold "Gordon Conference" type discussion covering accommodation and reactive uptake of water vapour and trace pollutant gases on condensed phase atmospheric materials. The scope was to review and define the current state of knowledge of accommodation coefficients for water vapour on water droplet and ice surfaces, and uptake of trace gas species on a variety of different surfaces characteristic of the atmospheric condensed phase particulate matter and cloud droplets. Twenty-six scientists participated in this meeting through presentations, discussions and the development of a consensus review. In this review we present an analysis of the state of knowledge on the thermal and mass accommodation coefficient for water vapour on aqueous droplets and ice and a survey of current state-of the-art of reactive uptake of trace gases on a range of liquid and solid atmospheric droplets and particles. The review recommends consistent definitions of the various parameters that are needed for quantitative representation of the range of gas/condensed surface kinetic processes important for the atmosphere and identifies topics that require additional research.

Air quality during the 2008 Beijing Olympics: secondary pollutants and regional impact

Abstract: . This paper presents the first results of the measurements of trace gases and aerosols at three surface sites in and outside Beijing before and during the 2008 Olympics. The official air pollution index near the Olympic Stadium and the data from our nearby site revealed an obvious association between air quality and meteorology and different responses of secondary and primary pollutants to the control measures. Ambient concentrations of vehicle-related nitrogen oxides (NOx) and volatile organic compounds (VOCs) at an urban site dropped by 25% and 20–45% in the first two weeks after full control was put in place, but the levels of ozone, sulfate and nitrate in PM2.5 increased by 16%, 64%, 37%, respectively, compared to the period prior to the full control; wind data and back trajectories indicated the contribution of regional pollution from the North China Plain. Air quality (for both primary and secondary pollutants) improved significantly during the Games, which were also associated with the changes in weather conditions (prolonged rainfall, decreased temperature, and more frequent air masses from clean regions). A comparison of the ozone data at three sites on eight ozone-pollution days, when the air masses were from the southeast-south-southwest sector, showed that regional pollution sources contributed >34–88% to the peak ozone concentrations at the urban site in Beijing. Regional sources also contributed significantly to the CO concentrations in urban Beijing. Ozone production efficiencies at two sites were low (~3 ppbv/ppbv), indicating that ozone formation was being controlled by VOCs. Compared with data collected in 2005 at a downwind site, the concentrations of ozone, sulfur dioxide (SO2), total sulfur (SO2+PM2.5 sulfate), carbon monoxide (CO), reactive aromatics (toluene and xylenes) sharply decreased (by 8–64%) in 2008, but no significant changes were observed for the concentrations of PM2.5, fine sulfate, total odd reactive nitrogen (NOy), and longer lived alkanes and benzene. We suggest that these results indicate the success of the government's efforts in reducing emissions of SO2, CO, and VOCs in Beijing, but increased regional emissions during 2005–2008. More stringent control of regional emissions will be needed for significant reductions of ozone and fine particulate pollution in Beijing.

Glyoxal processing by aerosol multiphase chemistry: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles

Abstract: . This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions that form secondary organic aerosol (SOA) in aqueous aerosol particles. Recent laboratory results on glyoxal reactions are reviewed and a consistent set of empirical reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds. Products of these processes include (a) oligomers, (b) nitrogen-containing products, (c) photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud) chemistry for the same conditions (liquid water content, particle size). The application of the new module including detailed chemical processes in a box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the predicted atmospheric relevance of SOA formation from glyoxal. During day time, a photochemical (most likely radical-initiated) process is the major SOA formation pathway forming ∼5 μg m−3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt). During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids) contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5 Glyoxal uptake into ammonium sulfate seed under dark conditions can be represented with a single reaction parameter keffupt that does not depend on aerosol loading or water content, which indicates a possibly catalytic role of aerosol water in SOA formation. However, the reversible nature of uptake under dark conditions is not captured by keffupt, and can be parameterized by an effective Henry's law constant including an equilibrium constant Kolig = 1000 (in ammonium sulfate solution). Such reversible glyoxal oligomerization contributes Sensitivity tests reveal five parameters that strongly affect the predicted SOA mass from glyoxal: (1) time scales to reach equilibrium states (as opposed to assuming instantaneous equilibrium), (2) particle pH, (3) chemical composition of the bulk aerosol, (4) particle surface composition, and (5) particle liquid water content that is mostly determined by the amount and hygroscopicity of aerosol mass and to a lesser extent by the ambient relative humidity. Glyoxal serves as an example molecule, and the conclusions about SOA formation in aqueous particles can serve for comparative studies of other molecules that form SOA as the result of multiphase chemical processing in aerosol water. This SOA source is currently underrepresented in atmospheric models; if included it is likely to bring SOA predictions (mass and O/C ratio) into better agreement with field observations.

A decadal regional and global trend analysis of the aerosol optical depth using a data-assimilation grade over-water MODIS and Level 2 MISR aerosol products

Abstract: . Using the ten-year (2000–2009) Data-Assimilation (DA) quality Terra MODIS and MISR aerosol products, as well as 7 years of Aqua MODIS, we studied both regional and global aerosol trends over oceans. This included both operational and data assimilation grade versions of the products. After correcting for what appears to be aerosol signal drift from the radiometric calibration of both MODIS instruments, we found MODIS and MISR agreed on a statistically negligible global trend of ±0.003/per decade. Our study also suggests that AODs over the Indian Bay of Bengal, east coast of Asia, and Arabian Sea show increasing trends of 0.07, 0.06, and 0.06 per decade for MODIS, respectively. These regional trends are considered as significant with a confidence level above 95%. Similar increasing trends were found from MISR, but with less relative magnitude. These trends reflect respective increases in the optical intensity of aerosol events in each region: anthropogenic aerosols over the east coast of China and Indian Bay of Bengal; and a stronger influence from dust events over the Arabian Sea. Negative AOD trends, low in confidence levels, are found off Central America, the east coast of North America, and the west coast of Africa, which indicate that longer periods of observation are necessary to be conclusive.

Cloud condensation nuclei in polluted air and biomass burning smoke near the mega-city Guangzhou, China – Part 1: Size-resolved measurements and implications for the modeling of aerosol particle hygroscopicity and CCN activity

Abstract: . Atmospheric aerosol particles serving as Cloud Condensation Nuclei (CCN) are key elements of the hydrological cycle and climate. We measured and characterized CCN in polluted air and biomass burning smoke during the PRIDE-PRD2006 campaign from 1–30 July 2006 at a rural site ~60 km northwest of the mega-city Guangzhou in southeastern China. CCN efficiency spectra (activated fraction vs. dry particle diameter; 20–290 nm) were recorded at water vapor supersaturations (S) in the range of 0.068% to 1.27%. The corresponding effective hygroscopicity parameters describing the influence of particle composition on CCN activity were in the range of κ≈0.1–0.5. The campaign average value of κ=0.3 equals the average value of κ for other continental locations. During a strong local biomass burning event, the average value of κ dropped to 0.2, which can be considered as characteristic for freshly emitted smoke from the burning of agricultural waste. At low S (≤0.27%), the maximum activated fraction remained generally well below one, indicating substantial portions of externally mixed CCN-inactive particles with much lower hygroscopicity – most likely soot particles (up to ~60% at ~250 nm). The mean CCN number concentrations (NCCN,S) ranged from 1000 cm−3 at S=0.068% to 16 000 cm−3 at S=1.27%, which is about two orders of magnitude higher than in pristine air. Nevertheless, the ratios between CCN concentration and total aerosol particle concentration (integral CCN efficiencies) were similar to the ratios observed in pristine continental air (~6% to ~85% at S=0.068% to 1.27%). Based on the measurement data, we have tested different model approaches for the approximation/prediction of NCCN,S. Depending on S and on the model approach, the relative deviations between observed and predicted NCCN,S ranged from a few percent to several hundred percent. The largest deviations occurred at low S with a simple power law. With a Kohler model using variable κ values obtained from individual CCN efficiency spectra, the relative deviations were on average less than ~10% and hardly exceeded 20%, confirming the applicability of the κ-Kohler model approach for efficient description of the CCN activity of atmospheric aerosols. Note, however, that different types of κ-parameters must be distinguished for external mixtures of CCN-active and -inactive aerosol particles (κa, κt, κcut). Using a constant average hygroscopicity parameter (κ=0.3) and variable size distributions as measured, the deviations between observed and predicted CCN concentrations were on average less than 20%. In contrast, model calculations using variable hygroscopicity parameters as measured and constant size distributions led to much higher deviations: ~70% for the campaign average size distribution, ~80% for a generic rural size distribution, and ~140% for a generic urban size distribution. These findings confirm earlier studies suggesting that aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. Depending on the required and applicable level of detail, the information and parameterizations presented in this study should enable efficient description of the CCN activity of atmospheric aerosols in detailed process models as well as in large-scale atmospheric and climate models.

Contributions from transport, solid fuel burning and cooking to primary organic aerosols in two UK cities

Abstract: . Organic matter frequently represents the single largest fraction of fine particulates in urban environments and yet the exact contributions from different sources and processes remain uncertain, owing in part to its substantial chemical complexity. Positive Matrix Factorisation (PMF) has recently proved to be a powerful tool for the purposes of source attribution and profiling when applied to ambient organic aerosol data from the Aerodyne Aerosol Mass Spectrometer (AMS). Here we present PMF analysis applied to AMS data from UK cities for the first time. Three datasets are analysed, with the focus on objectivity and consistency. The data were collected in London during the Regent's Park and Tower Environmental Experiment (REPARTEE) intensives and Manchester. These occurred during the autumn and wintertime, such that the primary fraction would be prominent. Ambiguities associated with rotationality within sets of potential solutions are explored and the most appropriate solution sets selected based on comparisons with external data. In addition to secondary organic aerosols, three candidate sources of primary organic aerosol (POA) were identified according to mass spectral and diurnal profiles; traffic emissions, cooking and solid fuel burning (for space heating). Traffic represented, on average, 40% of POA during colder conditions and exhibited a hydrocarbon-like mass spectrum similar to those previously reported. Cooking aerosols represented 34% of POA and through laboratory work, their profile was matched with that sampled from the heating of seed oils, rather than previously-published spectra derived from charbroiling. This suggests that in these locations, oil from frying may have contributed more to the particulate than the meat itself. Solid fuel aerosols represented 26% of POA during cold weather conditions but were not discernable during the first REPARTEE campaign, when conditions were warmer than the other campaigns. This factor showed features associated with biomass burning and occurred mainly at night. Grid-scale emission factors of the combustion aerosols suitable for use in chemical transport models were derived relative to CO and NOx. The traffic aerosols were found to be 20.5 μg m−3 ppm−1 relative to CO for Manchester and 31.6 μg m−3 ppm−1 relative to NOx for London. Solid fuel emissions were derived as 24.7 μg m−3 ppm−1 relative to CO for Manchester. These correspond to mass emission ratios of 0.018, 0.026 (as NO) and 0.021 respectively and are of a similar order to previously published estimates, derived from other regions or using other approaches.

An overview of the MILAGRO 2006 Campaign: Mexico City emissions and their transport and transformation

Abstract: . MILAGRO (Megacity Initiative: Local And Global Research Observations) is an international collaborative project to examine the behavior and the export of atmospheric emissions from a megacity. The Mexico City Metropolitan Area (MCMA) – one of the world's largest megacities and North America's most populous city – was selected as the case study to characterize the sources, concentrations, transport, and transformation processes of the gases and fine particles emitted to the MCMA atmosphere and to evaluate the regional and global impacts of these emissions. The findings of this study are relevant to the evolution and impacts of pollution from many other megacities. The measurement phase consisted of a month-long series of carefully coordinated observations of the chemistry and physics of the atmosphere in and near Mexico City during March 2006, using a wide range of instruments at ground sites, on aircraft and satellites, and enlisting over 450 scientists from 150 institutions in 30 countries. Three ground supersites were set up to examine the evolution of the primary emitted gases and fine particles. Additional platforms in or near Mexico City included mobile vans containing scientific laboratories and mobile and stationary upward-looking lidars. Seven instrumented research aircraft provided information about the atmosphere over a large region and at various altitudes. Satellite-based instruments peered down into the atmosphere, providing even larger geographical coverage. The overall campaign was complemented by meteorological forecasting and numerical simulations, satellite observations and surface networks. Together, these research observations have provided the most comprehensive characterization of the MCMA's urban and regional atmospheric composition and chemistry that will take years to analyze and evaluate fully. In this paper we review over 120 papers resulting from the MILAGRO/INTEX-B Campaign that have been published or submitted, as well as relevant papers from the earlier MCMA-2003 Campaign, with the aim of providing a road map for the scientific community interested in understanding the emissions from a megacity such as the MCMA and their impacts on air quality and climate. This paper describes the measurements performed during MILAGRO and the results obtained on MCMA's atmospheric meteorology and dynamics, emissions of gases and fine particles, sources and concentrations of volatile organic compounds, urban and regional photochemistry, ambient particulate matter, aerosol radiative properties, urban plume characterization, and health studies. A summary of key findings from the field study is presented.

Highly time-resolved chemical characterization of atmospheric submicron particles during 2008 Beijing Olympic Games using an Aerodyne High-Resolution Aerosol Mass Spectrometer

Abstract: . As part of Campaigns of Air Quality Research in Beijing and Surrounding Region-2008 (CAREBeijing-2008), an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed in urban Beijing to characterize submicron aerosol particles during the time of 2008 Beijing Olympic Games and Paralympic Games (24 July to 20 September 2008). The campaign mean PM1 mass concentration was 63.1 ± 39.8 μg m−3; the mean composition consisted of organics (37.9%), sulfate (26.7%), ammonium (15.9%), nitrate (15.8%), black carbon (3.1%), and chloride (0.87%). The average size distributions of the species (except BC) were all dominated by an accumulation mode peaking at about 600 nm in vacuum aerodynamic diameter, and organics was characterized by an additional smaller mode extending below 100 nm. Positive Matrix Factorization (PMF) analysis of the high resolution organic mass spectral dataset differentiated the organic aerosol into four components, i.e., hydrocarbon-like (HOA), cooking-related (COA), and two oxygenated organic aerosols (OOA-1 and OOA-2), which on average accounted for 18.1, 24.4, 33.7 and 23.7% of the total organic mass, respectively. The HOA was identified to be closely associated with primary combustion sources, while the COA mass spectrum and diurnal pattern showed similar characteristics to that measured for cooking emissions. The OOA components correspond to aged secondary organic aerosol. Although the two OOA components have similar elemental (O/C, H/C) compositions, they display differences in mass spectra and time series which appear to correlate with the different source regions sampled during the campaign. Back trajectory clustering analysis indicated that the southerly air flows were associated with the highest PM1 pollution during the campaign. Aerosol particles in southern airmasses were especially rich in inorganic and oxidized organic species. Aerosol particles in northern airmasses contained a large fraction of primary HOA and COA species, probably due to stronger influences from local emissions. The lowest concentration levels for all major species were obtained during the Olympic game days (8 to 24 August 2008), possibly due to the effects of both strict emission controls and favorable meteorological conditions.

Evaluation of the volatility basis-set approach for the simulation of organic aerosol formation in the Mexico City metropolitan area

Abstract: . New primary and secondary organic aerosol modules have been added to PMCAMx, a three dimensional chemical transport model (CTM), for use with the SAPRC99 chemistry mechanism based on recent smog chamber studies. The new modelling framework is based on the volatility basis-set approach: both primary and secondary organic components are assumed to be semivolatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. This new framework with the use of the new volatility basis parameters for low-NOx and high-NOx conditions tends to predict 4–6 times higher anthropogenic SOA concentrations than those predicted with the older generation of models. The resulting PMCAMx-2008 was applied in Mexico City Metropolitan Area (MCMA) for approximately a week during April 2003 during a period of very low regional biomass burning impact. The emission inventory, which uses as a starting point the MCMA 2004 official inventory, is modified and the primary organic aerosol (POA) emissions are distributed by volatility based on dilution experiments. The predicted organic aerosol (OA) concentrations peak in the center of Mexico City, reaching values above 40 μg m−3. The model predictions are compared with the results of the Positive Matrix Factorization (PMF) analysis of the Aerosol Mass Spectrometry (AMS) observations. The model reproduces both Hydrocarbon-like Organic Aerosol (HOA) and Oxygenated Organic Aerosol (OOA) concentrations and diurnal profiles. The small OA underprediction during the rush-hour periods and overprediction in the afternoon suggest potential improvements to the description of fresh primary organic emissions and the formation of the oxygenated organic aerosols, respectively, although they may also be due to errors in the simulation of dispersion and vertical mixing. However, the AMS OOA data are not specific enough to prove that the model reproduces the organic aerosol observations for the right reasons. Other combinations of contributions of primary and secondary organic aerosol production rates may lead to similar results. The model results strongly suggest that, during the simulated period, transport of OA from outside the city was a significant contributor to the observed OA levels. Future simulations should use a larger domain in order to test whether the regional OA can be predicted with current SOA parameterizations. Sensitivity tests indicate that the predicted OA concentration is especially sensitive to the volatility distribution of the emissions in the lower volatility bins.