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Airborne sunphotometer measurements are used to evaluate retrievals of extinction aerosol optical depth (AOD) from spatially coincident and temporally near-coincident measurements by the Ozone Monitoring Instrument (OMI) aboard the Aura satellite during the March 2006 Megacity Initiative-Local And Global Research Observations/Phase B of the Intercontinental Chemical Transport Experiment (MILAGRO/INTEX-B). The 14-channel NASA Ames Airborne Tracking Sunphotometer (AATS) flew on nine missions over the Gulf of Mexico and four in or near the Mexico City area. Retrievals of AOD from near-coincident AATS and OMI measurements are compared for three flights over the Gulf of Mexico for flight segments when the aircraft flew at altitudes 60–70 m above sea level, and for one flight over the Mexico City area where the aircraft was restricted to altitudes ~320–800 m above ground level over the rural area and ~550–750 m over the city. OMI-measured top of atmosphere (TOA) reflectances are routinely inverted to yield aerosol products such as AOD and aerosol absorption optical depth (AAOD) using two different retrieval algorithms: a near-UV (OMAERUV) and a multiwavelength (OMAERO) technique. This study uses the archived Collection 3 data products from both algorithms. In particular, AATS and OMI AOD comparisons are presented for AATS data acquired in 20 OMAERUV retrieval pixels (15 over water) and 19 OMAERO pixels (also 15 over water). At least four pixels for one of the over-water coincidences and all pixels for the over-land case were cloud-free. Coincident AOD retrievals from 17 pixels of the Moderate Resolution Imaging Spectroradiometer (MODIS) aboard Aqua are available for two of the over-water flights and are shown to agree with AATS AODs to within root mean square (RMS) differences of 0.00–0.06, depending on wavelength. Near-coincident ground-based AOD measurements from ground-based sun/sky radiometers operated as part of the Aerosol Robotic Network (AERONET) at three sites in and near Mexico City are also shown and are generally consistent with the AATS AODs (which exclude any AOD below the aircraft) both in magnitude and spectral dependence. The OMAERUV algorithm retrieves AODs corresponding to a non-absorbing aerosol model for all three over-water comparisons whereas the OMAERO algorithm retrieves best-fit AODs corresponding to an absorbing biomass-burning aerosol model for two of the three over-water cases. For the four cloud-free pixels in one over-water coincidence (10 March), the OMAERUV retrievals underestimate the AATS AODs by ~0.20, which exceeds the expected retrieval uncertainty, but retrieved AODs agree with AATS values within uncertainties for the other two over-water events. When OMAERO retrieves AODs corresponding to a biomass-burning aerosol over water, the values significantly overestimate the AATS AODs (by up to 0.55). For the Mexico City coincidence, comparisons are presented for a non-urban region ~50–70 km northeast of the city and for a site near the center of the city. OMAERUV retrievals are consistent with AERONET AOD magnitudes for the non-urban site, but are nearly double the AATS and AERONET AODs (with differences of up to 0.29) in the center of the city. Corresponding OMAERO retrievals exceed the AATS and/or AERONET AODs by factors of 3 to 10.
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In order to study particulate matter transport and transformation in the Megacity environment, fine particulate carbon was measured simultaneously at two supersites, suburban T1 and rural T2, downwind of Mexico City during the MILAGRO field campaign in March 2006. Organic carbon (OC), element carbon (EC), and total carbon (TC=OC+EC) were determined in near real-time using a Sunset semi-continuous OCEC field analyzer. The semi-empirical EC tracer method was used to derive primary organic carbon (POC) and secondary organic carbon (SOC). Diurnal variations of primary and secondary carbon were observed at T1 and T2, which resulted from boundary layer inversion and impacted by local traffic patterns. The majority of organic carbon particles at T1 and T2 were secondary. The SOC<sub>TC</sub>% (SOC%=SOC/TC×100%) at T1 ranged from 0.5–93.8% with an average of 63.5±17.2%. The SOC<sub>TC</sub>% at T2 ranged from 9.3–98.1% with an average of 67.4±12.4%. The average EC to PM<sub>2.5</sub> percentage (EC<sub>PM</sub>%=EC/PM<sub>2.5</sub>×100%) and OC<sub>PM</sub>% were 6.0% and 20.0% over the whole sampling time at T1. The POC to PM percentage (POC<sub>PM</sub>%) and SOC<sub>PM</sub>% were 3.7% and 16.3%, respectively at the same site. The maximum EC<sub>PM</sub>% was 21.2%, and the maximum OC<sub>PM</sub>% was 57.2% at T1. The maximum POC<sub>PM</sub>% was 12.9%, and the maximum SOC<sub>PM</sub>% was 49.7% at T1. Comparison of SOC and POC at T1 and T2 showed similar characteristics under favorable meteorological conditions, which indicated that transport from T1 towards T2 took place. Strong correlations between EC and carbon monoxide (CO) and odd nitrogen species (NO and NO<sub>x</sub>) were observed at T1. This indicated that EC had nearby sources, such as local traffic emissions. The EC/CO ratio derived by linear regression analysis, with units of μg C/m<sup>3</sup> and μg/m<sup>3</sup>, respectively, was 0.004 at T1. Correlations were also seen between OC and SOC vs. the sum of oxidants, such as O<sub>3</sub> and NO<sub>2</sub>, suggesting the secondary nature of carbons observed at T1.
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The hygroscopic properties of atmospheric aerosols are highly relevant for the quantification of radiative effects in the atmosphere, but also of interest for the assessment of particle health effects upon inhalation. This article reports measurements of aerosol particle hygroscopicity in the highly polluted urban atmosphere of Beijing, China in January 2005. The meteorological conditions corresponded to a relatively cold and dry atmosphere. Three different methods were used: 1) A combination of Humidifying Differential Mobility Particle Sizer (H-DMPS) and Twin Differential Mobility Particle Sizer (TDMPS) measurements, 2) A Hygroscopic Tandem Differential Mobility Analyzer (H-TDMA), and 3) A simplistic solubility model fed by chemical particle composition determined from Micro Orifice Uniform Deposit Impactor (MOUDI) samples. From the H-DMPS and TDMPS particle number size distributions, a size-resolved descriptive hygroscopic growth factor (DHGF) was determined for the relative humidities (RH) 55%, 77% and 90%, and particle diameters between 30 and 400 nm. In Beijing, the highest DHGFs were observed for accumulation mode particles, 1.40 (±0.03) at 90% RH. DHGF decreased significantly with particle size, reaching 1.04 (±0.15) at 30 nm. H-TDMA data also suggest a decrease in growth factor towards the biggest particles investigated (350 nm), associated with an increasing fraction of nearly hydrophobic particles. The agreement between the H-DMPS/TDMPS and H-TDMA methods was satisfactory in the accumulation mode size range (100–400 nm). In the Aitken mode range (<100 nm), the H-DMPS/TDMPS method yielded growth factors lower by up to 0.1 at 90% RH. The application of the solubility model based on measured chemical composition clearly reproduced the size-dependent trend in hygroscopic particle growth observed by the other methods. In the case of aerosol dominated by inorganic ions, the composition-derived growth factors tended to agree (± 0.05) or underestimate (up to 0.1) the values measured by the other two methods. In the case of aerosol dominated by organics, the reverse was true, with an overestimation of up to 0.2. The results shed light on the experimental and methodological uncertainties that are still connected with the determination of hygroscopic growth factors.
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Fourier Transform Infrared (FTIR) and X-ray Fluorescence (XRF) were used to measure organic functional groups and elements of submicron particles collected during MILAGRO in March 2006 on three platforms: the Mexico City urban area (SIMAT), the high altitude site at 4010 m (Altzomoni), and the NCAR C130 aircraft. Scanning Transmission X-ray Microscopy (STXM) and Near-Edge X-ray Absorption Fine Structure (NEXAFS) were applied to single particle organic functional group abundance analysis of particles simultaneously collected at SIMAT and C130. Correlations of elemental concentrations showed different groups of source-related elements at SIMAT, Altzomoni, and C130, suggesting different processes affecting the air masses sampled at the three platforms. Cluster analysis resulted in seven distinct clusters of FTIR spectra, with the last three clusters consisting of spectra collected almost exclusively on the C130 platform, reflecting the variety of sources contributing to C130 samples. Positive Matrix Factorization (PMF) of STXM-NEXAFS spectra identified three main factors representing soot, secondary, and biomass burning type spectra. PMF of FTIR spectra resulted in two fossil fuel combustion factors and one biomass burning factor, the former representative of source regions to the northeast and southwest of SIMAT. Alkane, carboxylic acid, amine, and alcohol functional groups were mainly associated with combustion related sources, while non-acid carbonyl groups were likely from biomass burning events. The majority of OM and O/C was attributed to combustion sources, although no distinction between direct emissions and atmospherically processed OM could be identified.
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A climatology of particle scattering properties in the wintertime High Arctic troposphere, including vertical distributions and effective radii, is presented. The measurements were obtained using a lidar and cloud radar located at Eureka, Nunavut Territory (80° N, 86° W). Four different particle groupings are considered: boundary-layer ice crystals, ice clouds, mixed-phase clouds, and aerosols. Two-dimensional histograms of occurrence probabilities against depolarization, radar/lidar colour ratio and height are given. Colour ratios are related to particle minimum dimensions (i.e., widths rather than lengths) using a Mie scattering model. Ice cloud crystals have effective radii spanning 25–220 µm, with larger particles observed at lower altitudes. Topographic blowing snow residuals in the boundary layer have the smallest crystals at 15–70 µm. Mixed-phase clouds have water droplets and ice crystal precipitation in the 5–40 µm and 40–220 µm ranges, respectively. Ice cloud crystals have depolarization decreasing with height. The depolarization trend is associated with the large ice crystal sub-population. Small crystals depolarize more than large ones in ice clouds at a given altitude, and show constant modal depolarization with height. Ice clouds in the mid-troposphere are sometimes observed to precipitate to the ground. Water clouds are constrained to the lower troposphere (0.5–3.5 km altitude). Aerosols are most abundant near the ground and are frequently mixed with the other particle types. The data are used to construct a classification chart for particle scattering in wintertime Arctic conditions.
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IASI measurements of spectral radiances made between the 1st April 2008 and the 15th April 2008 are compared with simulations performed using the RTTOV fast radiative transfer model utilizing regression coefficients based on different line-by-line models. The comparisons are performed within the framework of the European Centre for Medium-Range Weather Forecasts Integrated Forecast System using fields of temperature, water vapour and ozone obtained from short-range forecasts. Simulations are performed to assess the accuracy of the RTTOV computations and investigate relative differences between the line-by-line models and the quality of the spectroscopic databases on which the RTTOV coefficients are based.
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Ambient particle number size distributions spanning three years were used to characterize the frequency and intensity of atmospheric dust events in the urban areas of Beijing, China in combination with AERONET sun/sky radiometer data. Dust events were classified into two types based on the differences in particle number and volume size distributions and local weather conditions. This categorization was confirmed by aerosol index images, columnar aerosol optical properties, and vertical potential temperature profiles. During the type-1 events, dust particles dominated the total particle volume concentration (<10 μm), with a relative share over 70%. Anthropogenic particles in the Aitken and accumulation mode played a subordinate role here because of high wind speeds (>4 m s<sup>−1</sup>). The type-2 events occurred in rather stagnant air masses and were characterized by a lower volume fraction of coarse mode particles (on average, 55%). Columnar optical properties showed that the superposition of dust and anthropogenic aerosols in type-2 events resulted in a much higher AOD (average: 1.51) than for the rather pure dust aerosols in type-1 events (average AOD: 0.36). A discrepancy was found between the ground-based and column integrated particle volume size distributions, especially for the coarse mode particles. This discrepancy likely originates from both the limited comparability of particle volume size distributions derived from Sun photometer and in situ number size distributions, and the inhomogeneous vertical distribution of particles during dust events.
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The meso-scale chemistry-transport model CHIMERE is used to assess our understanding of major sources and formation processes leading to a fairly large amount of organic aerosols – OA, including primary OA (POA) and secondary OA (SOA) – observed in Mexico City during the MILAGRO field project (March 2006). Chemical analyses of submicron aerosols from aerosol mass spectrometers (AMS) indicate that organic particles found in the Mexico City basin contain a large fraction of oxygenated organic species (OOA) which have strong correspondence with SOA, and that their production actively continues downwind of the city. The SOA formation is modeled here by the one-step oxidation of anthropogenic (i.e. aromatics, alkanes), biogenic (i.e. monoterpenes and isoprene), and biomass-burning SOA precursors and their partitioning into both organic and aqueous phases. Conservative assumptions are made for uncertain parameters to maximize the amount of SOA produced by the model. The near-surface model evaluation shows that predicted OA correlates reasonably well with measurements during the campaign, however it remains a factor of 2 lower than the measured total OA. Fairly good agreement is found between predicted and observed POA within the city suggesting that anthropogenic and biomass burning emissions are reasonably captured. Consistent with previous studies in Mexico City, large discrepancies are encountered for SOA, with a factor of 2–10 model underestimate. When only anthropogenic SOA precursors were considered, the model was able to reproduce within a factor of two the sharp increase in OOA concentrations during the late morning at both urban and near-urban locations but the discrepancy increases rapidly later in the day, consistent with previous results, and is especially obvious when the column-integrated SOA mass is considered instead of the surface concentration. The increase in the missing SOA mass in the afternoon coincides with the sharp drop in POA suggesting a tendency of the model to excessively evaporate the freshly formed SOA. Predicted SOA concentrations in our base case were extremely low when photochemistry was not active, especially overnight, as the SOA formed in the previous day was mostly quickly advected away from the basin. These nighttime discrepancies were not significantly reduced when greatly enhanced partitioning to the aerosol phase was assumed. Model sensitivity results suggest that observed nighttime OOA concentrations are strongly influenced by a regional background SOA (~1.5 μg/m<sup>3</sup>) of biogenic origin which is transported from the coastal mountain ranges into the Mexico City basin. The presence of biogenic SOA in Mexico City was confirmed by SOA tracer-derived estimates that have reported 1.14 (±0.22) μg/m<sup>3</sup> of biogenic SOA at T0, and 1.35 (±0.24) μg/m<sup>3</sup> at T1, which are of the same order as the model. Consistent with other recent studies, we find that biogenic SOA does not appear to be underestimated significantly by traditional models, in strong contrast to what is observed for anthropogenic pollution. The relative contribution of biogenic SOA to predicted monthly mean SOA levels (traditional approach) is estimated to be more than 30% within the city and up to 65% at the regional scale which may help explain the significant amount of modern carbon in the aerosols inside the city during low biomass burning periods. The anthropogenic emissions of isoprene and its nighttime oxidation by NO<sub>3</sub> were also found to enhance the SOA mean concentrations within the city by an additional 15%. Our results confirm the large underestimation of the SOA production by traditional models in polluted regions (estimated as 10–20 tons within the Mexico City metropolitan area during the daily peak), and emphasize for the first time the role of biogenic precursors in this region, indicating that they cannot be neglected in urban modeling studies.
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The role of isoprene as a precursor to secondary organic aerosol (SOA) over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr<sup>−1</sup> and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of organic matter (OM) during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC) emissions from vegetation. However, during winter, our model strongly underestimates OM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning) of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr<sup>−1</sup>). The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Consequently, smog chamber experiments on SOA formation should be performed with different types of seed aerosols and without seed aerosols in order to derive an improved treatment of the absorption of SOA in the models. Consideration of a number of recent insights in isoprene SOA formation mechanisms reduces the tropospheric production of isoprene derived SOA over Europe from 0.4 Tg yr<sup>−1</sup> in our reference simulation to 0.1 Tg yr<sup>−1</sup>.
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Low-<i>Z</i> particle electron probe X-ray microanalysis (low-<i>Z</i> particle EPMA) shows powerful advantages for the characterization of ambient particulate matter in environmental and geological applications. By the application of the low-<i>Z</i> particle EPMA single particle analysis, an overall examination of 1800 coarse and fine particles (aerodynamic diameters: 2.5–10 μm and 1.0–2.5 μm, respectively) in six samples collected on 28 April–1 May 2006 in the marine boundary layer (MBL) of the Bohai Sea and Yellow Sea was conducted. Three samples (D1, D2, and D3) were collected along the Bohai Bay, Bohai Straits, and Yellow Sea near Korea during an Asian dust storm event while the other three samples (N3, N2, and N1) were collected on non-Asian dust (NAD) days. Based on X-ray spectral and secondary electron image data, 15 different types of particles were identified, in which soil-derived particles were encountered with the largest frequency, followed by (C, N, O)-rich droplets (likely the mixture of organic matter and NH<sub>4</sub>NO<sub>3</sub>), particles of marine origin, and carbonaceous, Fe-rich, fly ash, and (C, N, O, S)-rich droplet particles. Results show that during the Asian dust storm event relative abundances of the (C, N, O)-rich droplets and the nitrate-containing secondary soil-derived particles were markedly increased (on average by a factor of 4.5 and 2, respectively in PM<sub>2.5−10</sub> fraction and by a factor of 1.9 and 1.5, respectively in PM<sub>1.0−2.5</sub> fraction) in the MBL of the Bohai Sea and Yellow Sea, implying that Asian dust aerosols in springtime are an important carrier of gaseous inorganic nitrogen species, especially NO<sub>x</sub> (or HNO<sub>3</sub>) and NH<sub>3</sub>.
