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Ceburnis D,
Garbaras A, Szidat S,
Rinaldi M,
Fahrni S,
Perron N,
Wacker L,
Leinert S,
Remeikis V,
M. C. Facchini,
A. S. H. Prevot,
S. G. Jennings,
C. D. O&apos,
Dowd
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ABSTRACT: Dual carbon isotope analysis has been performed for the first time demonstrating a potential in organic matter apportionment between three principal sources: marine, terrestrial (non-fossil) and fossil fuel due to unique isotopic signatures. The results presented here, utilising combinations of dual carbon isotope analysis, provides a conclusive evidence of a dominant biogenic organic fraction to organic aerosol over biologically active oceans. In particular, the NE Atlantic, which is also subjected to notable anthropogenic influences via pollution transport processes, was found to contain 80% organic aerosol matter of biogenic origin directly linked to plankton emissions. The remaining carbonaceous aerosol was of fossil-fuel origin. By contrast, for polluted air advecting out from Europe into the NE Atlantic, the source apportionment is 30% marine biogenic, 40% fossil fuel, and 30% continental non-fossil fuel. The dominant marine organic aerosol source in the atmosphere has significant implications for climate change feedback processes.
Atmospheric Chemistry and Physics Discussions. 01/2011;
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ABSTRACT: A 3-D chemistry-transport model has been applied to the Mexico City metropolitan area to investigate the origin of elevated levels of non-fossil (NF) carbonaceous aerosols observed in this highly urbanized region. High time resolution measurements of the fine aerosol concentration and composition, and 12 or 24 h integrated 14C measurements of aerosol modern carbon have been performed in and near Mexico City during the March 2006 MILAGRO field experiment. The non-fossil carbon fraction (fCNF), which is lower than the measured modern fraction (fCM) due to the elevated 14C in the atmosphere caused by nuclear bomb testing, is estimated from the measured fCM and the available source information. The fCNF contained in PM1 total carbon (fCNFTC) ranged from 0.37 to 0.67 at the downtown location (T0), and from 0.50 to 0.86 at the suburban site T1. Substantially lower values (i.e. 0.24–0.49) were found for PM10 filters at T0 by an independent set of measurements, which are inconsistent with the modeled and known differences between the size ranges, suggesting higher than expected uncertainties in the measurement techniques of 14C. An increase in the non-fossil organic carbon (OC) fraction (fCNFOC) by 0.10–0.15 was observed for both sets of filters during periods with enhanced wildfire activity in comparison to periods when fires were suppressed by rain, which is consistent with the wildfire impacts estimated with other methods. Model results show that the relatively high fraction of non-fossil carbon found in Mexico City seems to arise from the combination of regional biogenic SOA, biomass burning OA, as well as non-fossil urban OA. Similar spatial and temporal variations for fCNFOC are predicted between the urban vs. suburban sites, and high-fire vs. low-fire periods. The absolute modeled values of fCNFOC are consistent with the PM10 dataset but lower than the PM1 filters. Resolving the 14C measurement discrepancies is necessary for further progress in model evaluation. The model simulations that included secondary organic aerosol (SOA) formation from semi-volatile and intermediate volatility (S/IVOC) vapors showed better skill in explaining both total OA mass and fCNFOC compared to simulations which only included SOA from VOCs. Urban sources of modern carbon are important in reducing or closing the gap between model and measurements, even though they are often neglected on the interpretation of 14C datasets. The fCNF of urban POA and SOA precursors is an important parameter that needs to be better constrained by measurements. Performing faster (≤3 h) 14C measurements in future campaigns is critical to further progress in this area. To our knowledge this is the first time that radiocarbon measurements are used together with aerosol mass spectrometer (AMS) organic components to assess the performance of a regional model for organic aerosols.
Atmospheric Chemistry and Physics Discussions. 01/2010;
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Perron N,
Sandradewi J,
M. R. Alfarra,
Lienemann P,
Gehrig R,
Kasper-Giebl A,
V. A. Lanz, Szidat S,
Ruff M,
Fahrni S,
Wacker L,
Baltensperger U,
A. S. H. Prévôt
[show abstract]
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ABSTRACT: A three-week long field campaign was carried out under autumnal meteorological conditions at four valley floor sites in the industrialised Swiss Rhone Valley. For one week of stable meteorological conditions, particulate matter with an aerodynamic diameter below 10 μm (PM10) was analysed from daily filters using ion chromatography, X-ray fluorescence, anhydrosugars and radiocarbon analysis of the organic and elemental matter (OM and EM, respectively). Furthermore, PM1 composition along the whole campaign was monitored in Massongex (a site near industries) by a seven-wavelength aethalometer and a quadrupole aerosol mass spectrometer (Q-AMS). At all sites, PM10 secondary inorganics and non-fossil EM and OM exhibited relatively stable concentrations over the selected days. On the contrary, PM10 fossil carbonaceous fractions, mineral dust components and several trace elements showed a significant decrease on Sunday, compared to the analysed working days. Their concentrations were also highly correlated. This evidenced the role of exhaust and resuspension emissions by heavy-duty vehicle traffic to the PM10 concentrations along the valley. In Massongex, organic matter and black carbon (BC) were the main contributors to PM1 over the campaign (accounting for 45% and 18% of PM1, respectively). An optical discrimination of BC highlighted the prevalence of fossil over wood-burning sources. Three types of PM1 organics could be identified by factor analysis: primary wood-burning organic aerosol (P-WBOA) dominated the PM1 carbonaceous fraction, followed by oxygenated organics (OOA) mostly representing secondary organics, and by traffic or possibly industry-related hydrocarbon-like organics (HOA) as the smallest carbonaceous contribution. Furthermore, unusually high contributions of fine chloride were detected at all sites. They were attributed to ammonium chloride (NH4Cl) in Massongex and represented the only significant component exclusively attributable to industrial emissions.
Atmospheric Chemistry and Physics Discussions. 01/2010;
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A. C. Aiken,
B. de Foy,
Wiedinmyer C,
P. F. DeCarlo,
I. M. Ulbrich,
M. N. Wehrli, Szidat S,
A. S. H. Prevot,
Noda J,
Wacker L, [......],
Laskin A,
Shutthanandan V,
Zheng J,
Zhang R,
Paredes-Miranda G,
W. P. Arnott,
L. T. Molina,
Sosa G,
Querol X,
J. L. Jimenez
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ABSTRACT: Submicron aerosol was analyzed during the MILAGRO field campaign in March 2006 at the T0 urban supersite in Mexico City with a High-Resolution Aerosol Mass Spectrometer (AMS) and complementary instrumentation. Positive Matrix Factorization (PMF) of high resolution AMS spectra identified a biomass burning organic aerosol (BBOA) component, which includes several large plumes that appear to be from forest fires within the region. Here, we show that the AMS BBOA concentration at T0 correlates with fire counts in the vicinity of Mexico City and that most of the BBOA variability is captured when the FLEXPART model is used for the dispersion of fire emissions as estimated from satellite fire counts. The resulting FLEXPART fire impact factor (FIF) correlates well with the observed BBOA, acetonitrile (CH3CN), levoglucosan, and potassium, indicating that wildfires in the region surrounding Mexico City are the dominant source of BBOA at T0 during MILAGRO. The impact of distant BB sources such as the Yucatan is small during this period. All fire tracers are correlated, with BBOA and levoglucosan showing little background, acetonitrile having a well-known tropospheric background of ~100–150 pptv, and PM2.5 potassium having a background of ~160 ng m−3 (two-thirds of its average concentration), which does not appear to be related to BB sources. We define two high fire periods based on satellite fire counts and FLEXPART-predicted FIFs. We then compare these periods with a low fire period when the impact of regional fires is about a factor of 5 smaller. Fire tracers are very elevated in the high fire periods whereas tracers of urban pollution do not change between these periods. Dust is also elevated during the high BB period but this appears to be coincidental due to the drier conditions and not driven by direct dust emission from the fires. The AMS oxygenated organic aerosol (OA) factor (OOA, mostly secondary OA or SOA) does not show an increase during the fire periods or a correlation with fire counts, FLEXPART-predicted FIFs or fire tracers, indicating that it is dominated by urban and/or regional sources and not by the fires near the MCMA. A new 14C aerosol dataset is presented. Both this new and a previously published dataset of 14C analysis suggest a similar BBOA contribution as the AMS and chemical mass balance (CMB), resulting in 13% higher non-fossil carbon during the high vs. low regional fire periods. The new dataset has ~15% more fossil carbon on average than the previously published one, and possible reasons for this discrepancy are discussed. During the low regional fire period, 38% of organic carbon (OC) and 28% total carbon (TC) are from non-fossil sources, suggesting the importance of urban and regional non-fossil carbon sources other than the fires, such as food cooking and regional biogenic SOA. The ambient BBOA/ΔCH3CN ratio is much higher in the afternoon when the wildfires are most intense than during the rest of the day. Also, there are large differences in the contributions of the different OA components to the surface concentrations vs. the integrated column amounts. Both facts may explain some apparent disagreements between BB impacts estimated from afternoon aircraft flights vs. those from 24-h ground measurements. We show that by properly accounting for the non-BB sources of K, all of the BB PM estimates from MILAGRO can be reconciled. Overall, the fires from the region near the MCMA are estimated to contribute 15–23% of the OA and 7–9% of the fine PM at T0 during MILAGRO, and 2–3% of the fine PM as an annual average. The 2006 MCMA emissions inventory contains a substantially lower impact of the forest fire emissions, although a fraction of these emissions occur just outside of the MCMA inventory area.
Atmospheric Chemistry and Physics. 01/2010;
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A. C. Aiken,
B. de Foy,
Wiedinmyer C,
P. F. DeCarlo,
I. M. Ulbrich,
M. N. Wehrli, Szidat S,
A. S. H. Prevot,
Noda J,
Wacker L, [......],
Laskin A,
Shutthanandan V,
Zheng J,
Zhang R,
Paredes-Miranda G,
W. P. Arnott,
L. T. Molina,
Sosa G,
Querol X,
J. L. Jimenez
[show abstract]
[hide abstract]
ABSTRACT: Submicron aerosol was analyzed during the MILAGRO field campaign in March 2006 at the T0 urban supersite in Mexico City with a High-Resolution Aerosol Mass Spectrometer (AMS) and complementary instrumentation. Positive Matrix Factorization (PMF) of high resolution AMS spectra identified a biomass burning OA (BBOA) component, which includes several large plumes that appear to be from forest fires within the region. Here, we show that the AMS BBOA concentration at T0 correlates with fire counts in the vicinity of Mexico City and that most of the BBOA variability is captured when the FLEXPART model is used for the dispersion of fire emissions as estimated from satellite fire counts. The resulting FLEXPART fire impact index correlates well with the observed BBOA, CH3CN, levoglucosan, and potassium, indicating that wildfires in the region surrounding Mexico City are the dominant source of BBOA at T0 during MILAGRO. The impact of distant BB sources such as the Yucatan is small during this period. All fire tracers are correlated, with BBOA and levoglucosan showing little background, acetonitrile having a well-known tropospheric background of ~100–150 ppt, and PM2.5 potassium having a background of ~160 ng m−3 (two-thirds of its average concentration), which does not appear to be related to BB sources. We define two high fire periods based on satellite fire counts and predicted fire impacts. We then compare these periods with a low fire period when the impact of regional fires is about a factor of 5 smaller. Fire tracers are very elevated in the high fire periods whereas tracers of urban pollution do not change between these periods. Dust is also elevated during the high BB period but this appears to be coincidental due to the drier conditions and not driven by direct dust emission from the fires. The AMS oxygenated OA factor (OOA, mostly secondary OA or SOA) does not show an increase during the fire periods or a correlation with fire counts, FLEXPART-predicted fire impacts or fire tracers, indicating that it is dominated by urban and/or regional sources and not by the fires near the MCMA. A new 14C aerosol dataset is presented. Both this new and a previously published dataset of 14C analysis suggest a similar BBOA contribution as the AMS and chemical mass balance (CMB), resulting in 15% higher modern carbon during the high vs. low regional fire periods. The new dataset has ~15% more fossil carbon on average than the previously published one, and possible reasons for this discrepancy are discussed. During the low regional fire period, 37% of organic carbon (OC) and 30% total carbon (TC) are from modern sources, suggesting the importance of urban and regional modern carbon sources other than the fires, such as food cooking and regional biogenic SOA. Overall, the fires from the region near the MCMA are estimated to contribute 15–23% of the OA and 7–9% of the fine PM at T0 during MILAGRO, and 2–3% of the fine PM as an annual average. The 2006 MCMA emissions inventory contains a substantially lower impact of the forest fire emissions, although a fraction of these emissions occur just outside of the MCMA inventory area. The ambient BBOA/ΔCH3CN ratio is much higher in the afternoon when the wildfires are most intense than during the rest of the day, which may explain some disagreements between BB impacts from afternoon aircraft flights and those from 24-h ground measurements. Finally, we show that there are large differences in the contributions of the different OA components to the surface concentrations vs. the integrated column amounts.
Atmospheric Chemistry and Physics Discussions. 01/2009;
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ABSTRACT: Particulate matter was collected at an urban site in Göteborg (Sweden) in February/March 2005 and in June/July 2006. Additional samples were collected at a rural site for the winter period. Total carbon (TC) concentrations were 2.1–3.6 μg m−3, 1.8–1.9 μg m−3, and 2.2–3.0 μg m−3 for urban/winter, rural/winter, and urban/summer conditions, respectively. Elemental carbon (EC), organic carbon (OC), water-insoluble OC (WINSOC), and water-soluble OC (WSOC) were analyzed for 14C in order to distinguish fossil from non-fossil emissions. As wood burning is the single major source of non-fossil EC, its contribution can be quantified directly. For non-fossil OC, the wood-burning fraction was determined independently by levoglucosan and 14C analysis and combined using Latin-hypercube sampling (LHS). For the winter period, the relative contribution of EC from wood burning to the total EC was >3 times higher at the rural site compared to the urban site, whereas the absolute concentrations of EC from wood burning were elevated only moderately at the rural compared to the urban site. Thus, the urban site is substantially more influenced by fossil EC emissions. For summer, biogenic emissions dominated OC concentrations most likely due to secondary organic aerosol (SOA) formation. During both seasons, a more pronounced fossil signal was observed for Göteborg than has previously been reported for Zurich, Switzerland. Analysis of air mass origin using back trajectories suggests that the fossil impact was larger when local sources dominated, whereas long-range transport caused an enhanced non-fossil signal. In comparison to other European locations, concentrations of levoglucosan and other monosaccharide anhydrides were low for the urban and the rural site in the area of Göteborg during winter.
Atmospheric Chemistry and Physics. 01/2009;
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Sandradewi J,
A. S. H. Prévôt,
M. R. Alfarra, Szidat S,
M. N. Wehrli,
Ruff M,
Weimer S,
V. A. Lanz,
Weingartner E,
Perron N,
Caseiro A,
Kasper-Giebl A,
Puxbaum H,
Wacker L,
Baltensperger U
[show abstract]
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ABSTRACT: Residential wood combustion has only recently been recognized as a major contributor to air pollution in Switzerland and in other European countries. A source apportionment method using the aethalometer light absorption parameters was applied to five winter campaigns at three sites in Switzerland: a village with high wood combustion activity in winter, an urban background site and a highway site. The particulate mass from traffic (PMtraffic) and wood burning (PMwb) emissions obtained with this model compared fairly well with results from the 14C source apportionment method. PMwb from the model was also compared to well known wood smoke markers such as anhydrosugars (levoglucosan and mannosan) and fine mode potassium, as well as to a marker recently suggested from the Aerodyne aerosol mass spectrometer (mass fragment m/z 60). Additionally the anhydrosugars were compared to the 14C results and were shown to be comparable to literature values from wood burning emission studies using different types of wood (hardwood, softwood). The levoglucosan to PMwb ratios varied much more strongly between the different campaigns (4–13%) compared to mannosan to PMwb with a range of 1–1.5%. Possible uncertainty aspects for the various methods and markers are discussed.
Atmospheric Chemistry and Physics Discussions. 01/2008;
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[show abstract]
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ABSTRACT: Particulate matter was collected at an urban site in Göteborg (Sweden) in February/March 2005 and in June/July 2006. Additional samples were collected at a rural site for the winter period. Elemental carbon (EC), organic carbon (OC), water-insoluble OC (WINSOC), and water-soluble OC (WSOC) were analyzed for 14C in order to distinguish fossil from non-fossil emissions. As wood burning is the single major source of non-fossil EC, its contribution can be quantified directly. For non-fossil OC, the wood burning fraction was determined independently by levoglucosan and 14C analysis and combined using Latin-hypercube sampling (LHS). For the winter period, the relative contribution of EC from wood burning to the total EC was >3 times higher at the rural site compared to the urban site, whereas the absolute concentrations of EC from wood burning were comparable at both sites. Thus, the urban site is substantially more influenced by fossil EC emissions. For summer, biogenic emissions dominated OC concentrations most likely due to secondary organic aerosol (SOA) formation. During both seasons, a more pronounced fossil signal was observed for Göteborg than has previously been reported for Zurich, Switzerland. Analysis of air mass origin using back trajectories suggests that the fossil impact was larger when local sources dominated, whereas long-range transport caused an enhanced non-fossil signal. In comparison to other European locations, concentrations of levoglucosan and other monosaccharide anhydrides were low for the urban and the rural site in the area of Göteborg during winter. The comparison of summer and winter results provides insight into the annual cycle of anthropogenic vs. biogenic contributions to the atmospheric aerosol.
Atmospheric Chemistry and Physics Discussions. 01/2008;
