scholarly journals Modeling anthropogenically controlled secondary organic aerosols in a megacity: a simplified framework for global and climate models

2011 ◽  
Vol 4 (4) ◽  
pp. 901-917 ◽  
Author(s):  
A. Hodzic ◽  
J. L. Jimenez
Keyword(s):  
Mexico City ◽  
Biomass Burning ◽  
Climate Models ◽  
Transport Model ◽  
Anthropogenic Pollution ◽  
Temporal Variations ◽  
Anthropogenic Sources ◽  
Organic Vapors ◽  
Chemistry Transport Model ◽  
Evolution Of Oxygen

Abstract. A simplified parameterization for secondary organic aerosol (SOA) formation in polluted air and biomass burning smoke is tested and optimized in this work, towards the goal of a computationally inexpensive method to calculate pollution and biomass burning SOA mass and hygroscopicity in global and climate models. A regional chemistry-transport model is used as the testbed for the parameterization, which is compared against observations from the Mexico City metropolitan area during the MILAGRO 2006 field experiment. The empirical parameterization is based on the observed proportionality of SOA concentrations to excess CO and photochemical age of the airmass. The approach consists in emitting an organic gas as lumped SOA precursor surrogate proportional to anthropogenic or biomass burning CO emissions according to the observed ratio between SOA and CO in aged air, and reacting this surrogate with OH into a single non-volatile species that condenses to form SOA. An emission factor of 0.08 g of the lumped SOA precursor per g of CO and a rate constant with OH of 1.25 × 10−11 cm3 molecule−1 s−1 reproduce the observed average SOA mass within 30 % in the urban area and downwind. When a 2.5 times slower rate is used (5 × 10−12 cm3 molecule−1 s−1) the predicted SOA amount and temporal evolution is nearly identical to the results obtained with SOA formation from semi-volatile and intermediate volatility primary organic vapors according to the Robinson et al. (2007) formulation. Our simplified method has the advantage of being much less computationally expensive than Robinson-type methods, and can be used in regions where the emissions of SOA precursors are not yet available. As the aged SOA/ΔCO ratios are rather consistent globally for anthropogenic pollution, this parameterization could be reasonably tested in and applied to other regions. The evolution of oxygen-to-carbon ratio was also empirically modeled and the predicted levels were found to be in reasonable agreement with observations. The potential enhancement of biogenic SOA by anthropogenic pollution, which has been suggested to play a major role in global SOA formation, is also tested using two simple parameterizations. Our results suggest that the pollution enhancement of biogenic SOA could provide additional SOA, but does not however explain the concentrations or the spatial and temporal variations of measured SOA mass in the vicinity of Mexico City, which appears to be controlled by anthropogenic sources. The contribution of the biomass burning to the predicted SOA is less than 10% during the studied period.

scholarly journals Modeling anthropogenically-controled secondary organic aerosols in a megacity: a simplified framework for global and climate models

2011 ◽  
Vol 4 (2) ◽  
pp. 869-905
Author(s):  
A. Hodzic ◽  
J. L. Jimenez
Keyword(s):  
Mexico City ◽  
Biomass Burning ◽  
Climate Models ◽  
Transport Model ◽  
Anthropogenic Pollution ◽  
Organic Aerosol ◽  
Temporal Variations ◽  
Anthropogenic Sources ◽  
Organic Vapors ◽  
Chemistry Transport Model

Abstract. A simplified parameterization for secondary organic aerosol (SOA) formation in polluted air and biomass burning smoke is tested and optimized in this work, towards the goal of a computationally inexpensive method to calculate pollution and biomass burning SOA in global and climate models. A regional chemistry-transport model is used as the testbed for the parameterization, which is compared against observations from the Mexico City metropolitan area during the MILAGRO 2006 field experiment. The empirical parameterization is based on the observed proportionality of SOA concentrations to excess CO and photochemical age of the airmass. The approach consists in emitting an organic gas as lumped SOA precursor surrogate proportional to anthropogenic or biomass burning CO emissions according to the observed ratio between SOA and CO in aged air, and reacting this surrogate with OH into a single non-volatile species that condenses to form SOA. An emission factor of 0.08 g of the lumped SOA precursor per g of CO and a rate constant with OH of 1.25 × 10−11 cm3 molecule−1 s−1 reproduce the observed average SOA mass within 30% in the urban area and downwind. When a 2.5 times slower rate is used (5 × 10−12 cm3 molecule−1 s−1) the predicted SOA amount and temporal evolution is nearly identical to the results obtained with SOA formation from semi-volatile and intermediate volatility primary organic vapors according to the Robinson et al. (2007) formulation. Our simplified method has the advantage of being much less computationally expensive than Robinson-type methods, and can be used in regions where the emissions of SOA precursors are not yet available. As the aged pollution SOA/ΔCO ratios are rather consistent globally, this parameterization could be reasonably tested in and applied to other regions. The potential enhancement of biogenic SOA by anthropogenic pollution, which has been suggested to play a major role in global SOA formation, is also tested using two simple parameterizations. Our results suggest that the pollution enhancement of biogenic SOA could provide several μg m−3 of additional SOA, but does not however explain the concentrations or especially the spatial and temporal variations of measured SOA mass in the vicinity of Mexico City, which appears to be controlled by anthropogenic sources. The contribution of the biomass burning to the predicted SOA is less than 10% during the study period.

scholarly journals Can 3-D models explain the observed fractions of fossil and non-fossil carbon in and near Mexico City?

2010 ◽  
Vol 10 (22) ◽  
pp. 10997-11016 ◽  
Author(s):  
A. Hodzic ◽  
J. L. Jimenez ◽  
A. S. H. Prévôt ◽  
S. Szidat ◽  
J. D. Fast ◽  
...  
Keyword(s):  
Mexico City ◽  
Biomass Burning ◽  
Transport Model ◽  
Measurement Techniques ◽  
Independent Set ◽  
Temporal Variations ◽  
Total Carbon ◽  
High Time Resolution ◽  
Carbonaceous Aerosols ◽  
Fossil Carbon

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 (fNF), which is lower than the measured modern fraction (fM) due to the elevated 14C in the atmosphere caused by nuclear bomb testing, is estimated from the measured fM and the source-dependent information on modern carbon enrichment. The fNF contained in PM1 total carbon analyzed by a US team (fNFTC) ranged from 0.37 to 0.67 at the downtown location, and from 0.50 to 0.86 at the suburban site. Substantially lower values (i.e. 0.24–0.49) were found for PM10 filters downtown by an independent set of measurements (Swiss team), 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 (fNFOC) 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 in about equal proportions of regional biogenic SOA, biomass burning POA and SOA, as well as non-fossil urban POA and SOA. Predicted spatial and temporal variations for fNFOCare similar to those in the measurements between the urban vs. suburban sites, and high-fire vs. low-fire periods. The absolute modeled values of fNFOC are consistent with the Swiss dataset but lower than the US dataset. 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 improved closure for the total OA mass compared to simulations which only included SOA from VOCs, providing a more realistic basis to evaluate the fNF predictions. fNFOC urban sources of modern carbon are important in reducing or removing the difference in fNF between model and measurements, even though they are often neglected on the interpretation of 14C datasets. An underprediction of biomass burning POA by the model during some mornings also explains a part of the model-measurement differences. The fNF 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.

scholarly journals Influences of hydroxyl radicals (OH) on top-down estimates of the global and regional methane budgets

2020 ◽  
Author(s):  
Yuanhong Zhao ◽  
Marielle Saunois ◽  
Philippe Bousquet ◽  
Xin Lin ◽  
Antoine Berchet ◽  
...  
Keyword(s):  
Spatial Distribution ◽  
Climate Models ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Temporal Variations ◽  
Oh Radicals ◽  
Chemical Transport Model ◽  
Top Down ◽  
Ch4 Emissions ◽  
The Impact

Abstract. The hydroxyl radical (OH), which is the dominant sink of methane (CH4), plays a key role to close the global methane budget. Previous research that assessed the impact of OH changes on the CH4 budget mostly relied on box modeling inversions with a very simplified atmospheric transport and no representation of the heterogeneous spatial distribution of OH radicals. Here using a variational Bayesian inversion framework and a 3D chemical transport model, LMDz, combined with 10 different OH fields derived from chemistry-climate models (CCMI experiment), we evaluate the influence of OH burden, spatial distribution, and temporal variations on the global CH4 budget. The global tropospheric mean CH4-reaction-weighted [OH] ([OH]GM-CH4) ranges 10.3–16.3 × 105 molec cm−3 across 10 OH fields during the early 2000s, resulting in inversion-based global CH4 emissions between 518 and 757 Tg yr−1. The uncertainties in CH4 inversions induced by the different OH fields are comparable to, or even larger than the uncertainty typically given by bottom-up and top-down estimates. Based on the LMDz inversions, we estimate that a 1 %-increase in OH burden leads to an increase of 4 Tg yr−1 in the estimate of global methane emissions, which is about 25 % smaller than what is estimated by box-models. The uncertainties in emissions induced by OH are largest over South America, corresponding to large inter-model differences of [OH] in this region. From the early to the late 2000s, the optimized CH4 emissions increased by 21.9 ± 5.7 Tg yr−1 (16.6–30.0 Tg yr−1), of which ~ 25 % (on average) is contributed by −0.5 to +1.8 % increase in OH burden. If the CCMI models represent the OH trend properly over the 2000s, our results show that a higher increasing trend of CH4 emissions is needed to match the CH4 observations compared to the CH4 emission trend derived using constant OH. This study strengthens the importance to reach a better representation of OH burden and of OH spatial and temporal distributions to reduce the uncertainties on the global CH4 budget.

scholarly journals Sources of Springtime Surface Black Carbon in the Arctic: An Adjoint Analysis

2017 ◽  
Author(s):  
Ling Qi ◽  
Qinbin Li ◽  
Daven K. Henze ◽  
Hsien-Liang Tseng ◽  
Cenlin He
Keyword(s):  
Natural Gas ◽  
Black Carbon ◽  
Biomass Burning ◽  
Transport Model ◽  
Lower Troposphere ◽  
Anthropogenic Sources ◽  
The Arctic ◽  
Anthropogenic Source ◽  
Gas Flaring ◽  
Arctic Front

Abstract. We quantify source contributions to springtime (April 2008) surface black carbon (BC) in the Arctic by interpreting surface observations of BC at five receptor sites (Denali, Barrow, Alert, Zeppelin, and Summit) using a global chemical transport model (GEOS-Chem) and its adjoint. Contributions to BC at Barrow, Alert, and Zeppelin are dominated by Asian anthropogenic sources (40–43 %) before April 18 and by Siberian open biomass burning emissions (29–41 %) afterward. In contrast, Summit, a mostly free tropospheric site, has predominantly an Asian anthropogenic source contribution (24–68 %, with an average of 45 %). We compute the adjoint sensitivity of BC concentrations at the five sites during a pollution episode (April 20–25) to global emissions from March 1 to April 25. The associated contributions are the combined results of these sensitivities and BC emissions. Local and regional anthropogenic sources in Alaska are the largest anthropogenic sources of BC at Denali (63 %), and natural gas flaring emissions in the Western Extreme North of Russia (WENR) are the largest anthropogenic sources of BC at Zeppelin (26 %) and Alert (13 %). We find that long-range transport of emissions from Beijing-Tianjin-Hebei (also known as Jing-Jin-Ji), the biggest urbanized region in Northern China, contribute significantly (~ 10 %) to surface BC across the Arctic. On average it takes ~ 12 days for Asian anthropogenic emissions and Siberian biomass burning emissions to reach Arctic lower troposphere, supporting earlier studies. Natural gas flaring emissions from the WENR reach Zeppelin in about a week. We find that episodic, direct transport events dominate BC at Denali (87 %), a site outside the Arctic front, a strong transport barrier. The relative contribution of direct transport to surface BC within the Arctic front is much smaller (~ 50 % at Barrow and Zeppelin and ~ 10 % at Alert). The large contributions from Asian anthropogenic sources are predominately in the form of ‘chronic’ pollution (~ 40 % at Barrow and 65 % at Alert and 57 % at Zeppelin) on 1–2 month timescales. As such, it is likely that previous studies using 5- or 10-day trajectory analyses strongly underestimated the contribution from Asia to surface BC in the Arctic. Both finer temporal resolution of biomass burning emissions and accounting for the Wegener-Bergeron-Findeisen (WBF) process in wet scavenging improve the source attribution estimates.

scholarly journals The influence of biogenic emissions on upper-tropospheric methanol as revealed from space

2007 ◽  
Vol 7 (24) ◽  
pp. 6119-6129 ◽  
Author(s):  
G. Dufour ◽  
S. Szopa ◽  
D. A. Hauglustaine ◽  
C. D. Boone ◽  
C. P. Rinsland ◽  
...  
Keyword(s):  
Northern Hemisphere ◽  
Biomass Burning ◽  
Transport Model ◽  
Tropospheric Chemistry ◽  
Biogenic Emissions ◽  
Chemistry Transport Model ◽  
Mixing Ratios ◽  
Oxygenated Compounds ◽  
Global Space ◽  
The Impact

Abstract. The distribution and budget of oxygenated organic compounds in the atmosphere and their impact on tropospheric chemistry are still poorly constrained. Near-global space-borne measurements of seasonally resolved upper tropospheric profiles of methanol (CH3OH) by the ACE Fourier transform spectrometer provide a unique opportunity to evaluate our understanding of this important oxygenated organic species. ACE-FTS observations from March 2004 to August 2005 period are presented. These observations reveal the pervasive imprint of surface sources on upper tropospheric methanol: mixing ratios observed in the mid and high latitudes of the Northern Hemisphere reflect the seasonal cycle of the biogenic emissions whereas the methanol cycle observed in the southern tropics is highly influenced by biomass burning emissions. The comparison with distributions simulated by the state-of-the-art global chemistry transport model, LMDz-INCA, suggests that: (i) the background methanol (high southern latitudes) is correctly represented by the model considering the measurement uncertainties; (ii) the current emissions from the continental biosphere are underestimated during spring and summer in the Northern Hemisphere leading to an underestimation of modelled upper tropospheric methanol; (iii) the seasonal variation of upper tropospheric methanol is shifted to the fall in the model suggesting either an insufficient destruction of CH3OH (due to too weak chemistry and/or deposition) in fall and winter months or an unfaithful representation of transport; (iv) the impact of tropical biomass burning emissions on upper tropospheric methanol is rather well reproduced by the model. This study illustrates the potential of these first global profile observations of oxygenated compounds in the upper troposphere to improve our understanding of their global distribution, fate and budget.

Climatological Biomass Burning CO – Where it comes from and where it goes.

2020 ◽  
Author(s):  
Nikos Daskalakis ◽  
Maria Kanakidou ◽  
Mihalis Vrekoussis ◽  
Laura Gallardo
Keyword(s):  
Biomass Burning ◽  
Transport Model ◽  
Source Region ◽  
Atmospheric Composition ◽  
Anthropogenic Sources ◽  
3 Dimensional ◽  
Source Regions ◽  
The World ◽  
Transport Patterns ◽  
The Impact

<p>Carbon Monoxide (CO) is an important atmospheric trace gas, and among the key O<sub>3</sub> precursors in the troposphere, alongside NO<sub>x</sub> and VOCs. It is among the most important sinks of OH radical in the atmosphere, which controls lifetime of CH<sub>4</sub> — a major greenhouse gas. Biomass burning sources contribute about 25% to the global emissions of CO, with the remaining CO being either emitted from anthropogenic sources, or being chemically formed in the atmosphere. Because of CO tropospheric lifetime is about two months; it can be transported in the atmosphere thus its sources have a hemispheric impact on atmospheric composition.</p><p>The extent of the impact of biomass burning to remote areas of the world through long range transport is here investigated using the global 3-dimensional chemistry transport model TM4-ECPL. For this, tagged biomass burning CO tracers from the 13 different HTAP (land) source regions are used in the model in order to evaluate the contribution of each source region to the CO concentrations in the 170 HTAP receptor regions that originate from biomass burning. The global simulations cover the period 1994—2015 in order to derive climatological transport patterns for CO and assess the contribution of each of the source regions to each of the receptor regions in the global troposphere. The CO simulations are evaluated by comparison with satellite observations from MOPITT and ground based observations from WDCGG. We show the significant impact of biomass burning emissions to the most remote regions of the world.</p>

scholarly journals Interannual variability of tropospheric composition: the influence of changes in emissions, meteorology and clouds

2010 ◽  
Vol 10 (5) ◽  
pp. 2491-2506 ◽  
Author(s):  
A. Voulgarakis ◽  
N. H. Savage ◽  
O. Wild ◽  
P. Braesicke ◽  
P. J. Young ◽  
...  
Keyword(s):  
Interannual Variability ◽  
Biomass Burning ◽  
Strong Influence ◽  
Transport Model ◽  
Global Scale ◽  
Meteorological Conditions ◽  
Shortwave Radiation ◽  
Chemistry Transport Model ◽  
Attribution Analysis ◽  
Emission Changes

Abstract. We have run a chemistry transport model (CTM) to systematically examine the drivers of interannual variability of tropospheric composition during 1996–2000. This period was characterised by anomalous meteorological conditions associated with the strong El Niño of 1997–1998 and intense wildfires, which produced a large amount of pollution. On a global scale, changing meteorology (winds, temperatures, humidity and clouds) is found to be the most important factor driving interannual variability of NO2 and ozone on the timescales considered. Changes in stratosphere-troposphere exchange, which are largely driven by meteorological variability, are found to play a particularly important role in driving ozone changes. The strong influence of emissions on NO2 and ozone interannual variability is largely confined to areas where intense biomass burning events occur. For CO, interannual variability is almost solely driven by emission changes, while for OH meteorology dominates, with the radiative influence of clouds being a very strong contributor. Through a simple attribution analysis for 1996–2000 we conclude that changing cloudiness drives 25% of the interannual variability of OH over Europe by affecting shortwave radiation. Over Indonesia this figure is as high as 71%. Changes in cloudiness contribute a small but non-negligible amount (up to 6%) to the interannual variability of ozone over Europe and Indonesia. This suggests that future assessments of trends in tropospheric oxidizing capacity should account for interannual variability in cloudiness, a factor neglected in many previous studies.

scholarly journals On the hiatus in the acceleration of tropical upwelling since the beginning of the 21st century

2014 ◽  
Vol 14 (7) ◽  
pp. 9951-9973 ◽  
Author(s):  
J. Aschmann ◽  
J. P. Burrows ◽  
C. Gebhardt ◽  
A. Rozanov ◽  
R. Hommel ◽  
...  
Keyword(s):  
21St Century ◽  
Climate Models ◽  
Lower Stratosphere ◽  
Transport Model ◽  
Early Period ◽  
Satellite Observations ◽  
Implicit Assumption ◽  
Apparent Contradiction ◽  
Chemistry Transport Model ◽  
Global Surface

Abstract. Chemistry–climate models predict an acceleration of the upwelling branch of the Brewer–Dobson circulation as a consequence of increasing global surface temperatures, resulting from elevated levels of atmospheric greenhouse gases. The observed decrease of ozone in the tropical lower stratosphere during the last decades of the 20th century is consistent with the anticipated acceleration of upwelling. However, more recent satellite observations of ozone reveal that this decrease has unexpectedly stopped in the first decade of the 21st century, challenging the implicit assumption of a continuous acceleration of tropical upwelling. In this study we use three decades of chemistry-transport-model simulations (1980–2013) to investigate this phenomenon and resolve this apparent contradiction. Our model reproduces the observed tropical lower stratosphere ozone record, showing a significant decrease in the early period followed by a statistically robust trend-change after 2002. We demonstrate that this trend-change is correlated with corresponding changes in the vertical transport and conclude that a hiatus in the acceleration of tropical upwelling occurred during the last decade.

scholarly journals Constraining CO<sub>2</sub> emissions from open biomass burning by satellite observations of co-emitted species: a method and its application to wildfires in Siberia

2014 ◽  
Vol 14 (2) ◽  
pp. 3099-3168 ◽  
Author(s):  
I. B. Konovalov ◽  
E. V. Berezin ◽  
P. Ciais ◽  
G. Broquet ◽  
M. Beekmann ◽  
...  
Keyword(s):  
Co2 Emissions ◽  
Biomass Burning ◽  
Transport Model ◽  
Regional Scale ◽  
Satellite Observations ◽  
Emission Model ◽  
Chemistry Transport Model ◽  
Conversion Factors ◽  
Fire Emissions ◽  
Global Emission

Abstract. A method to constrain carbon dioxide (CO2) emissions from open biomass burning by using satellite observations of co-emitted species and a chemistry-transport model (CTM) is proposed and applied to the case of wildfires in Siberia. CO2 emissions are assessed by means of an emission model assuming a direct relationship between the biomass burning rate (BBR) and the Fire Radiative Power (FRP) derived from the MODIS measurements. The key features of the method are (1) estimating the FRP-to-BBR conversion factors (α) for different vegetative land cover types by assimilating the satellite observations of co-emitted species into the CTM, (2) optimal combination of the estimates of α derived independently from satellite observations of different species (CO and aerosol in this study), and (3) estimation of the diurnal cycle of the fire emissions directly from the FRP measurements. Values of α for forest and grassland fires in Siberia and their uncertainties are estimated by using the IASI carbon monoxide (CO) retrievals and the MODIS aerosol optical depth (AOD) measurements combined with outputs from the CHIMERE mesoscale chemistry transport model. The constrained CO emissions are validated through comparison of the respective simulations with the independent data of ground based CO measurements at the ZOTTO site. Using our optimal regional-scale estimates of the conversion factors (which are found to be in agreement with the earlier published estimates obtained from local measurements of experimental fires), the total CO2 emissions from wildfires in Siberia in 2012 are estimated to be in the range from 262 to 477 Tg C, with the optimal (maximum likelihood) value of 354 Tg C. Sensitivity test cases featuring different assumptions regarding the injection height and diurnal variations of emissions indicate that the derived estimates of the total CO2 emissions in Siberia are robust with respect to the modelling options (the different estimates vary within less than 10% of their magnitude). The obtained CO2 emission estimates for several years are compared with the independent estimates provided by the GFED3.1 and GFASv1.0 global emission inventories. It is found that our "top-down" estimates for the total annual biomass burning CO2 emissions in the period from 2007 to 2011 in Siberia are by factors of 2.3 and 1.7 larger than the respective bottom-up estimates; these discrepancies cannot be fully explained by uncertainties in our estimates. There are also considerable differences in the spatial distribution of the different emission estimates; some of those differences have a systematic character and require further analysis.

scholarly journals Can 3-D models explain the observed fractions of fossil and non-fossil carbon in and near Mexico City?

2010 ◽  
Vol 10 (6) ◽  
pp. 14513-14556 ◽  
Author(s):  
A. Hodzic ◽  
J. L. Jimenez ◽  
A. S. H. Prévôt ◽  
S. Szidat ◽  
J. D. Fast ◽  
...  
Keyword(s):  
Mexico City ◽  
Transport Model ◽  
Measurement Techniques ◽  
Independent Set ◽  
Temporal Variations ◽  
Total Carbon ◽  
High Time Resolution ◽  
Carbonaceous Aerosols ◽  
Source Information ◽  
Fossil Carbon

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.

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