Secondary Organic Aerosol Production Rate Research Articles

On the evolution of sub- and super-saturated water uptake of secondary organic aerosol in chamber experiments from mixed precursors

Abstract. To better understand the chemical controls of sub- and super-saturated aerosol water uptake, we designed and conducted a series of chamber experiments to investigate the evolution of secondary organic aerosol (SOA) particle physicochemical properties during photo-oxidation of single and mixed biogenic (α-pinene, isoprene) and anthropogenic (o-cresol) volatile organic compounds (VOCs) in the presence of ammonium sulfate seeds. During the 6 h experiments, the cloud condensation nuclei (CCN) activity at super-saturation of water (0.1 %–0.5 %), hygroscopic growth factor at 90 % relative humidity (RH), and non-refractory PM1 chemical composition were recorded concurrently. Attempts to use the hygroscopicity parameter κ to reconcile water uptake ability below and above water saturation from various VOC precursor systems were made, aiming to predict the CCN activity from the sub-saturated hygroscopicity. The thermodynamic model AIOMFAC (aerosol inorganic-organic mixtures functional groups activity coefficients) was used to simulate κ values of model compound mixtures to compare with the observation and to isolate the controlling factors of water uptake at different RHs. The sub- and super-saturated water uptake (in terms of both κHTDMA and κCCN) were mainly controlled by the SOA mass fraction, which depended on the SOA production rate of the precursors, and the SOA composition played a second-order role. For the reconciliation of κHTDMA and κCCN, the κHTDMA/κCCN ratio increased with the SOA mass fraction and this was observed in all investigated single and mixed VOC systems, independent of initial VOC concentrations and sources. For all VOC systems, the mean κHTDMA of aerosol particles was ∼25 % lower than the κCCN at the beginning of the experiments with inorganic seeds. With the increase of condensed SOA on inorganic seed particles throughout the experiments, the discrepancy of κHTDMA and κCCN became weaker (down to ∼0 %) and finally the mean κHTDMA was ∼60 % higher than κCCN on average when the SOA mass fraction approached ∼0.8. As indicated by AIOMFAC model simulations, non-ideality alone cannot fully explain the κ discrepancy at high SOA mass fraction (0.8). A good agreement in κCCN between model and observation was achieved by doubling the molecular weight of the model compounds or by reducing the dry particle size in the CCN counter. This indicates that the evaporation of semi-volatile organics in the CCN counter together with non-ideality could have led to the observed κ discrepancy. As a result, the predicted CCN number concentrations from the κHTDMA and particle number size distribution were ∼10 % lower than CCN counter measurement on average at the beginning, and further even turned to an overestimation of ∼20 % on average when the SOA mass fraction was ∼0.8. This chemical composition-dependent performances of the κ-Köhler approach on CCN prediction can introduce a variable uncertainty in predicting cloud droplet numbers from the sub-saturated water uptake, the influence of which on models still needs to be investigated.

Phase state of secondary organic aerosol in chamber photo-oxidation of mixed precursors

Abstract. The phase behaviour of aerosol particles plays a profound role in atmospheric physicochemical processes, influencing their physical and optical properties and further impacting climate and air quality. However, understanding of the aerosol phase state is still incomplete, especially that of multicomponent particles which contain inorganic compounds and secondary organic aerosol (SOA) from mixed volatile organic compound (VOC) precursors. We report measurements conducted in the Manchester Aerosol Chamber (MAC) to investigate the aerosol rebounding tendency, measured as the bounce fraction, as a surrogate of the aerosol phase state during SOA formation from photo-oxidation of biogenic (α-pinene and isoprene) and anthropogenic (o-cresol) VOCs and their binary mixtures on deliquescent ammonium sulfate seed. Aerosol phase state is dependent on relative humidity (RH) and chemical composition (key factors determining aerosol water uptake). Liquid (bounce fraction; BF < 0.2) at RH > 80 % and nonliquid behaviour (BF > 0.8) at RH < 30 % were observed, with a liquid-to-nonliquid transition with decreasing RH between 30 % and 80 %. This RH-dependent phase behaviour (RHBF=0.2,0.5,0.8) increased towards a maximum, with an increasing organic–inorganic mass ratio (MRorg/inorg) during SOA formation evolution in all investigated VOC systems. With the use of comparable initial ammonium sulfate seed concentration, the SOA production rate of the VOC systems determines the MRorg/inorg and, consequently, the change in the phase behaviour. Although less important than RH and MRorg/inorg, the SOA composition plays a second-order role, with differences in the liquid-to-nonliquid transition at moderate MRorg/inorg of ∼1 observed between biogenic-only (anthropogenic-free) and anthropogenic-containing VOC systems. Considering the combining role of the RH and chemical composition in aerosol phase state, the BF decreased monotonically with increasing hygroscopic growth factor (GF), and the BF was ∼0 when GF was larger than 1.15. The real atmospheric consequences of our results are that any processes changing ambient RH or MRorg/inorg (aerosol liquid water) will influence their phase state. Where abundant anthropogenic VOCs contribute to SOA, compositional changes in SOA may influence phase behaviour at moderate organic mass fraction (∼50 %) compared with purely biogenic SOA. Further studies are needed on more complex and realistic atmospheric mixtures.

Secondary Organic Aerosol Formation of Fleet Vehicle Emissions in China: Potential Seasonality of Spatial Distributions.

Vehicle emissions are an important source of urban particular matter. To investigate the secondary organic aerosol (SOA) formation potential of real-world vehicle emissions, we exposed on-road air in Beijing to hydroxyl radicals generated in an oxidation flow reactor (OFR) under high-NOx conditions on-board a mobile laboratory and characterized SOA and their precursors with a suite of state-of-the-art instrumentation. The OFR produced 10-170 μg m-3 of SOA with a maximum SOA formation potential of 39-50 μg m-3 ppmv-1 CO that occurred following an integrated OH exposure of (1.3-2.0) × 1011 molecules cm-3 s. The results indicate relatively shorter photochemical ages for maximum SOA production than previous OFR results obtained under low-NOx conditions. Such timescales represent the balance of functionalization and fragmentation, possibly resulting in different spatial distributions of SOA in different seasons as the oxidant level changes. The detected precursors may explain as much as 13% of the observed SOA with the remaining plausibly contributed by the oxidation of undetected intermediate-volatility organic compounds. Extrapolation of the results suggests an annual SOA production rate of 0.78 Tg yr-1 from mobile gasoline sources in China, highlighting the importance of effective regulation of gaseous vehicular precursors to improve air quality in the future.

Photolysis Controls Atmospheric Budgets of Biogenic Secondary Organic Aerosol.

Secondary organic aerosol (SOA) accounts for a large fraction of the tropospheric particulate matter. Although SOA production rates and mechanisms have been extensively investigated, loss pathways remain uncertain. Most large-scale chemistry and transport models account for mechanical deposition of SOA but not chemical losses such as photolysis. There is also a paucity of laboratory measurements of SOA photolysis, which limits how well photolytic losses can be modeled. Here, we show, through a combined experimental and modeling approach, that photolytic loss of SOA mass significantly alters SOA budget predictions. Using environmental chamber experiments at variable relative humidity between 0 and 60%, we find that SOA produced from several biogenic volatile organic compounds undergoes photolysis-induced mass loss at rates between 0 and 2.2 ± 0.4% of nitrogen dioxide (NO2) photolysis, equivalent to average atmospheric lifetimes as short as 10 h. We incorporate our photolysis rates into a regional chemical transport model to test the sensitivity of predicted SOA mass concentrations to photolytic losses. The addition of photolysis causes a ∼50% reduction in biogenic SOA loadings over the Amazon, indicating that photolysis exerts a substantial control over the atmospheric SOA lifetime, with a likely dependence upon the SOA molecular composition and thus production mechanisms.

Secondary organic aerosol formation from smoldering and flaming combustion of biomass: a box model parametrization based on volatility basis set

Abstract. Residential wood combustion remains one of the most important sources of primary organic aerosols (POA) and secondary organic aerosol (SOA) precursors during winter. The overwhelming majority of these precursors have not been traditionally considered in regional models, and only recently were lignin pyrolysis products and polycyclic aromatics identified as the principal SOA precursors from flaming wood combustion. The SOA yields of these components in the complex matrix of biomass smoke remain unknown and may not be inferred from smog chamber data based on single-compound systems. Here, we studied the ageing of emissions from flaming and smoldering-dominated wood fires in three different residential stoves, across a wide range of ageing temperatures (−10, 2 and 15 ∘C) and emission loads. Organic gases (OGs) acting as SOA precursors were monitored by a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS), while the evolution of the aerosol properties during ageing in the smog chamber was monitored by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). We developed a novel box model based on the volatility basis set (VBS) to determine the volatility distributions of the oxidation products from different precursor classes found in the emissions, grouped according to their emission pathways and SOA production rates. We show for the first time that SOA yields in complex emissions are consistent with those reported in literature from single-compound systems. We identify the main SOA precursors in both flaming and smoldering wood combustion emissions at different temperatures. While single-ring and polycyclic aromatics are significant precursors in flaming emissions, furans generated from cellulose pyrolysis appear to be important for SOA production in the case of smoldering fires. This is especially the case at high loads and low temperatures, given the higher volatility of furan oxidation products predicted by the model. We show that the oxidation products of oxygenated aromatics from lignin pyrolysis are expected to dominate SOA formation, independent of the combustion or ageing conditions, and therefore can be used as promising markers to trace ageing of biomass smoke in the field. The model framework developed herein may be generalizable for other complex emission sources, allowing determination of the contributions of different precursor classes to SOA, at a level of complexity suitable for implementation in regional air quality models.

The roles of volatile organic compound deposition and oxidation mechanisms in determining secondary organic aerosol production: a global perspective using the UKCA chemistry–climate model (vn8.4)

Abstract. The representation of volatile organic compound (VOC) deposition and oxidation mechanisms in the context of secondary organic aerosol (SOA) formation are developed in the United Kingdom Chemistry and Aerosol (UKCA) chemistry–climate model. Impacts of these developments on both the global SOA budget and model agreement with observations are quantified. Firstly, global model simulations were performed with varying VOC dry deposition and wet deposition fluxes. Including VOC dry deposition reduces the global annual-total SOA production rate by 2 %–32 %, with the range reflecting uncertainties in surface resistances. Including VOC wet deposition reduces the global annual-total SOA production rate by 15 % and is relatively insensitive to changes in effective Henry's law coefficients. Without precursor deposition, simulated SOA concentrations are lower than observed with a normalised mean bias (NMB) of −51 %. Hence, including SOA precursor deposition worsens model agreement with observations even further (NMB =-66 %). Secondly, for the anthropogenic and biomass burning VOC precursors of SOA (VOCANT∕BB), model simulations were performed by (a) varying the parent hydrocarbon reactivity, (b) varying the number of reaction intermediates, and (c) accounting for differences in volatility between oxidation products from various pathways. These changes were compared to a scheme where VOCANT∕BB adopts the reactivity of a monoterpene (α-pinene), and is oxidised in a single-step mechanism with a fixed SOA yield. By using the chemical reactivity of either benzene, toluene, or naphthalene for VOCANT∕BB, the global annual-total VOCANT∕BB oxidation rate changes by −3 %, −31 %, or −66 %, respectively, compared to when using α-pinene. Increasing the number of reaction intermediates, by introducing a peroxy radical (RO2), slightly slows the rate of SOA formation, but has no impact on the global annual-total SOA production rate. However, RO2 undergoes competitive oxidation reactions, forming products with substantially different volatilities. Accounting for the differences in product volatility between RO2 oxidation pathways increases the global SOA production rate by 153 % compared to using a single SOA yield. Overall, for relatively reactive compounds such as toluene and naphthalene, the reduction in reactivity for VOCANT∕BB oxidation is outweighed by accounting for the difference in volatility of RO2 products, leading to a net increase in the global annual-total SOA production rate of 85 % and 145 %, respectively, and improvements in model agreement (NMB of −46 % and 56 %, respectively). However, for benzene, the reduction in VOCANT∕BB oxidation is not outweighed by accounting for the difference in SOA yield pathways, leading to a small change in the global annual-total SOA production rate of −3 %, and a slight worsening of model agreement with observations (NMB =-77 %). These results highlight that variations in both VOC deposition and oxidation mechanisms contribute to substantial uncertainties in the global SOA budget and model agreement with observations.

The impact of biogenic, anthropogenic, and biomass burning volatile organic compound emissions on regional and seasonal variations in secondary organic aerosol

Abstract. The global secondary organic aerosol (SOA) budget is highly uncertain, with global annual SOA production rates, estimated from global models, ranging over an order of magnitude and simulated SOA concentrations underestimated compared to observations. In this study, we use a global composition-climate model (UKCA) with interactive chemistry and aerosol microphysics to provide an in-depth analysis of the impact of each VOC source on the global SOA budget and its seasonality. We further quantify the role of each source on SOA spatial distributions, and evaluate simulated seasonal SOA concentrations against a comprehensive set of observations. The annual global SOA production rates from monoterpene, isoprene, biomass burning, and anthropogenic precursor sources is 19.9, 19.6, 9.5, and 24.6 Tg (SOA) a−1, respectively. When all sources are included, the SOA production rate from all sources is 73.6 Tg (SOA) a−1, which lies within the range of estimates from previous modelling studies. SOA production rates and SOA burdens from biogenic and biomass burning SOA sources peak during Northern Hemisphere (NH) summer. In contrast, the anthropogenic SOA production rate is fairly constant all year round. However, the global anthropogenic SOA burden does have a seasonal cycle which is lowest during NH summer, which is probably due to enhanced wet removal. Inclusion of the new SOA sources also accelerates the ageing by condensation of primary organic aerosol (POA), making it more hydrophilic, leading to a reduction in the POA lifetime. With monoterpene as the only source of SOA, simulated SOA and total organic aerosol (OA) concentrations are underestimated by the model when compared to surface and aircraft measurements. Model agreement with observations improves with all new sources added, primarily due to the inclusion of the anthropogenic source of SOA, although a negative bias remains. A further sensitivity simulation was performed with an increased anthropogenic SOA reaction yield, corresponding to an annual global SOA production rate of 70.0 Tg (SOA) a−1. Whilst simulated SOA concentrations improved relative to observations, they were still underestimated in urban environments and overestimated further downwind and in remote environments. In contrast, the inclusion of SOA from isoprene and biomass burning did not improve model–observations biases substantially except at one out of two tropical locations. However, these findings may reflect the very limited availability of observations to evaluate the model, which are primarily located in the NH mid-latitudes where anthropogenic emissions are high. Our results highlight that, within the current uncertainty limits in SOA sources and reaction yields, over the NH mid-latitudes, a large anthropogenic SOA source results in good agreement with observations. However, more observations are needed to establish the importance of biomass burning and biogenic sources of SOA in model agreement with observations.

Air‐Sea exchange of biogenic volatile organic compounds and the impact on aerosol particle size distributions

AbstractWe report simultaneous, underway eddy covariance measurements of the vertical flux of isoprene, total monoterpenes, and dimethyl sulfide (DMS) over the Northern Atlantic Ocean during fall. Mean isoprene and monoterpene sea‐to‐air vertical fluxes were significantly lower than mean DMS fluxes. While rare, intense monoterpene sea‐to‐air fluxes were observed, coincident with elevated monoterpene mixing ratios. A statistically significant correlation between isoprene vertical flux and short wave radiation was not observed, suggesting that photochemical processes in the surface microlayer did not enhance isoprene emissions in this study region. Calculations of secondary organic aerosol production rates (PSOA) for mean isoprene and monoterpene emission rates sampled here indicate that PSOA is on average <0.1 μg m−3 d−1. Despite modest PSOA, low particle number concentrations permit a sizable role for condensational growth of monoterpene oxidation products in altering particle size distributions and the concentration of cloud condensation nuclei during episodic monoterpene emission events from the ocean.

A modeling study of secondary organic aerosol formation from sesquiterpenes using the STOCHEM global chemistry and transport model

AbstractSesquiterpenes are one of the precursors of secondary organic aerosol (SOA) which can be an important global sources of organic aerosol (OA). Updating the chemistry scheme in the global chemistry transport model by incorporating an oxidation mechanism for β‐caryophyllene (representing all sesquiterpenes), adding global sesquiterpene emissions of 29 Tg/yr, and revising global monoterpene emissions up to 162 Tg/yr [Guenther et al., 2012] led to an increase of SOA burden by 95% and SOA production rate by 106% relative to the base case described in Utembe et al. [2011]. Including the emissions of sesquiterpenes resulted in increase of SOA burden of 0.11 Tg and SOA production rate of 12.9 Tg/yr relative to the base case. The highest concentrations of sesquiterpene‐derived SOA (by up to 1.2 μg/m3) were found over central Africa and South America, the regions having high levels of biogenic emissions with significant biomass burning. In the updated model simulation, the multigeneration oxidation products from sesquiterpenes and monoterpenes transported above the boundary layer and condensed to the aerosol phase at higher altitude led to an increase of OA by up to 30% over the tropics and northern midlatitude to higher altitude. The model evaluation showed an underestimation of model OA mostly for the campaigns dominated by regional anthropogenic pollution. The increase of SOA production from sesquiterpenes reduced the discrepancies between modeled and observed OA concentrations over the remote and rural areas. The increase of SOA concentrations by up to 200% from preindustrial to present scenarios was found over the tropical oceans.

Model analysis of secondary organic aerosol over China with a regional air quality modeling system (RAMS-CMAQ)

The regional air quality modeling system RAMS-CMAQ was updated to incorporate secondary organic aerosol (SOA) production from isoprene and sesquiterpene and to account for the SOA production rate dependence on NOx and SOA aging. The system was then used to simulate spatiotemporal distributions of SOA concentration and its major constituents over China in winter. Modeled monthly mean SOA concentrations were high in central and eastern China and low in western regions. The highest SOA appeared in regions from Beijing–Tianjin–Hebei (BTH) to the middle reaches of the Yangtze River and areas from Sichuan Basin to the southwest border of China, where SOA contributions were less than 10% of the organic aerosol (OA). The lowest concentration was in the Qinghai–Tibet Plateau, accounting for 20%–30% of OA. It is notable that contributions from anthropogenic precursors to SOA were significant in winter, especially the wide areas of central and eastern China with contributions generally varying from 50% to 80% of the total SOA. Beijing was used as an example location representative of the heavily polluted BTH area for analysis of major components of SOA. Though the modeled concentration of SOA was still underestimated compared to the observations, it still showed that xylene and toluene were the two greatest contributors to anthropogenic SOA, which was in agreement with the observations. SOA produced from monoterpene was the greatest contributor to biogenic SOA due to the high mass yield of monoterpene, followed by isoprene. More than 57% of SOAs were aged, which may increase the extinction effect of SOA.

Global modeling of SOA: the use of different mechanisms for aqueous-phase formation

Abstract. There is growing interest in the formation of secondary organic aerosol (SOA) through condensed aqueous-phase reactions. In this study, we use a global model (IMPACT) to investigate the potential formation of SOA in the aqueous phase. We compare results from several multiphase process schemes with detailed aqueous-phase reactions to schemes that use a first-order gas-to-particle formation rate based on uptake coefficients. The predicted net global SOA production rate in cloud water ranges from 13.1 Tg yr−1 to 46.8 Tg yr−1 while that in aerosol water ranges from −0.4 Tg yr−1 to 12.6 Tg yr−1. The predicted global burden of SOA formed in the aqueous phase ranges from 0.09 Tg to 0.51 Tg. A sensitivity test to investigate two representations of cloud water content from two global models shows that increasing cloud water by an average factor of 2.7 can increase the net SOA production rate in cloud water by a factor of 4 at low altitudes (below approximately 900 hPa). We also investigated the importance of including dissolved Fe chemistry in cloud water aqueous reactions. Adding these reactions increases the formation rate of aqueous-phase OH by a factor of 2.6 and decreases the amount of global aqueous SOA formed by 31%. None of the mechanisms discussed here is able to provide a best fit for all observations. Rather, the use of an uptake coefficient method for aerosol water and a multi-phase scheme for cloud water provides the best fit in the Northern Hemisphere and the use of multiphase process scheme for aerosol and cloud water provides the best fit in the tropics. The model with Fe chemistry underpredicts oxalate measurements in all regions. Finally, the comparison of oxygen-to-carbon (O / C) ratios estimated in the model with those estimated from measurements shows that the modeled SOA has a slightly higher O / C ratio than the observed SOA for all cases.

Modeling SOA formation from the oxidation of intermediate volatility <i>n</i>-alkanes

Abstract. The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8–C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.

Impact of model grid spacing on regional- and urban- scale air quality predictions of organic aerosol

Abstract. Regional-scale chemical transport model predictions of urban organic aerosol to date tend to be biased low relative to observations, a limitation with important implications for applying such models to human exposure health studies. We used a nested version of Environment Canada's AURAMS model (42- to- 15- to- 2.5-km nested grid spacing) to predict organic aerosol concentrations for a temporal and spatial domain corresponding to the Border Air Quality and Meteorology Study (BAQS-Met), an air-quality field study that took place in the southern Great Lakes region in the summer of 2007. The use of three different horizontal grid spacings allowed the influence of this parameter to be examined. A domain-wide average for the 2.5-km domain and a matching 15-km subdomain yielded very similar organic aerosol averages (4.8 vs. 4.3 μg m−3, respectively). On regional scales, secondary organic aerosol dominated the organic aerosol composition and was adequately resolved by the 15-km model simulation. However, the shape of the organic aerosol concentration histogram for the Windsor urban station improved for the 2.5-km simulation relative to those from the 42- and 15-km simulations. The model histograms for the Bear Creek and Harrow rural stations were also improved in the high concentration "tail" region. As well the highest-resolution model results captured the midday 4 July organic-aerosol plume at Bear Creek with very good temporal correlation. These results suggest that accurate simulation of urban and large industrial plumes in the Great Lakes region requires the use of a high-resolution model in order to represent urban primary organic aerosol emissions, urban VOC emissions, and the secondary organic aerosol production rates properly. The positive feedback between the secondary organic aerosol production rate and existing organic mass concentration is also represented more accurately with the highest-resolution model. Not being able to capture these finer-scale features may partly explain the consistent negative bias reported in the literature when urban-scale organic aerosol evaluations are made using coarser-scale chemical transport models.

Photochemical processing of organic aerosol at nearby continental sites: contrast between urban plumes and regional aerosol

Abstract. As part of the BAQS-Met 2007 field campaign, Aerodyne time-of-flight aerosol mass spectrometers (ToF-AMS) were deployed at two sites in southwestern Ontario from 17 June to 11 July 2007. One instrument was located at Harrow, ON, a rural, agriculture-dominated area approximately 40 km southeast of the Detroit/Windsor/Windsor urban area and 5 km north of Lake Erie. The second instrument was located at Bear Creek, ON, a rural site approximately 70 km northeast of the Harrow site and 50 km east of Detroit/Windsor. Positive matrix factorization analysis of the combined organic mass spectral dataset yields factors related to secondary organic aerosol (SOA), direct emissions, and a factor tentatively attributed to the reactive uptake of isoprene and/or condensation of its early generation reaction products. This is the first application of PMF to simultaneous AMS measurements at different sites, an approach which allows for self-consistent, direct comparison of the datasets. Case studies are utilized to investigate processing of SOA from (1) fresh emissions from Detroit/Windsor and (2) regional aerosol during periods of inter-site flow. A strong correlation is observed between SOA/excess CO and photochemical age as represented by the NOx/NOy ratio for Detroit/Windsor outflow. Although this correlation is not evident for more aged air, measurements at the two sites during inter-site transport nevertheless show evidence of continued atmospheric processing by SOA production. However, the rate of SOA production decreases with airmass age from an initial value of ~10.1 μg m−3 ppmvCO−1 h−1 for the first ~10 h of plume processing to near-zero in an aged airmass (i.e. after several days). The initial SOA production rate is comparable to the observed rate in Mexico City over similar timescales.

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.