Predicting diurnal variability of fine inorganic aerosols and their gas-phase precursors near downtown Mexico City

International audiencePartitioning of semi-volatile nitrate and ammonium between the gas and particulate phases is studied combining two thermodynamic models that explicitly include crustal elements and simulate both branches (deliquescence, efflorescence) of aerosol behavior and measurements taken near downtown Mexico City during a field campaign conducted in February?March, 2005. Overall, no significant differences between model predictions (within 30% of error) are observed for particulate ammonium (PM2.5, PM1). In cases of moderate to high RH (40?70%), mostly occurring during the 1st and 2nd daily sampling periods (06:00?10:00 h, 10:00?14:00 h, LST), 4 h PM2.5 nitrate measurements are predicted within 30%. When RH drops below 30%, characteristic of the afternoon sampling periods (14:00-18:00 h), the efflorescence branch is most consistent with observed PM nitrate. Residual error analysis of these low RH cases suggest that aerosol nitrate loading or sulfate-to-nitrate molar ratio control phase behavior, hence the partitioning of semi-volatile PM2.5 nitrate in gas and particulate phases. Finally, inclusion of crustal elements in the modeling framework reduces the error in predicted PM2.5 ammonium by 25%. These findings, if generally applicable, can help improve air quality modeling in nitrate deficient environments

Simulating the oxygen content of ambient organic aerosol with the 2D volatility basis set

A module predicting the oxidation state of organic aerosol (OA) has been developed using the two-dimensional volatility basis set (2D-VBS) framework. This model is an extension of the 1D-VBS framework and tracks saturation concentration and oxygen content of organic species during their atmospheric lifetime. The host model, a one-dimensional Lagrangian transport model, is used to simulate air parcels arriving at Finokalia, Greece during the Finokalia Aerosol Measurement Experiment in May 2008 (FAME-08). Extensive observations were collected during this campaign using an aerosol mass spectrometer (AMS) and a thermodenuder to determine the chemical composition and volatility, respectively, of the ambient OA. Although there are several uncertain model parameters, the consistently high oxygen content of OA measured during FAME-08 (O:C = 0.8) can help constrain these parameters and elucidate OA formation and aging processes that are necessary for achieving the high degree of oxygenation observed. The base-case model reproduces observed OA mass concentrations (measured mean = 3.1 μg m<sup>−3</sup>, predicted mean = 3.3 μg m<sup>−3</sup>) and O:C (predicted O:C = 0.78) accurately. A suite of sensitivity studies explore uncertainties due to (1) the anthropogenic secondary OA (SOA) aging rate constant, (2) assumed enthalpies of vaporization, (3) the volatility change and number of oxygen atoms added for each generation of aging, (4) heterogeneous chemistry, (5) the oxidation state of the first generation of compounds formed from SOA precursor oxidation, and (6) biogenic SOA aging. Perturbations in most of these parameters do impact the ability of the model to predict O:C well throughout the simulation period. By comparing measurements of the O:C from FAME-08, several sensitivity cases including a high oxygenation case, a low oxygenation case, and biogenic SOA aging case are found to unreasonably depict OA aging, keeping in mind that this study does not consider possibly important processes like fragmentation that may offset mass gains and affect the prediction bias. On the other hand, many of the cases chosen for this study predict average O:C estimates that are consistent with the observations, illustrating the need for more thorough experimental characterizations of OA parameters including the enthalpy of vaporization and oxidation state of the first generation of SOA products. The ability of the model to predict OA concentrations is less sensitive to perturbations in the model parameters than its ability to predict O:C. In this sense, quantifying O:C with a predictive model and constraining it with AMS measurements can reduce uncertainty in our understanding of OA formation and aging

Size-resolved CCN distributions and activation kinetics of aged continental and marine aerosol

We present size-segregated measurements of cloud condensation nucleus (CCN) activity of aged aerosol sampled at Finokalia, Crete, during the Finokalia Aerosol Measurement Experiment of summer 2007 (FAME07). From analysis of the data, hygroscopicity and activation kinetics distributions are derived. The CCN are found to be highly hygroscopic, (expressed by a size- and time- averaged hygroscopicity parameter κ ∼ 0.22), with the majority of particles activating at ~0.5–0.6 % supersaturation. Air masses originating from Central-Eastern Europe tend to be associated with higher CCN concentrations and slightly lower hygroscopicity (κ ∼ 0.18) than for other airmass types. The particles were always well mixed, as reflected by the high activation ratios and narrow hygroscopicity distribution widths. Smaller particles (~40 nm) were found to be more hygroscopic (~0.1κ units higher) than the larger ones (~100 nm). The particles with diameters less than 80 nm exhibited a diurnal hygroscopicity cycle (with κ peaking at ~14 h local time), consistent with photochemical aging and volatilization of less hygroscopic material from the aerosol. Use of bulk chemical composition and the aerosol number distribution results in excellent CCN closure when applying Köhler theory in its simplest form. Using asymptotic and threshold droplet growth analysis, the "aged" organics present in the aerosol were found not to suppress or delay the water uptake kinetics of particles in this environment

Evaluation of an entraining droplet activation parameterization using in situ cloud data

This study investigates the ability of a droplet activation parameterization (which considers the effects of entrainment and mixing) to reproduce observed cloud droplet number concentration (CDNC) in ambient clouds. Predictions of the parameterization are compared against cloud averages of CDNC from ambient cumulus and stratocumulus clouds sampled during CRYSTAL‐FACE (Key West, Florida, July 2002) and CSTRIPE (Monterey, California, July 2003), respectively. The entrainment parameters required by the parameterization are derived from the observed liquid water content profiles. For the cumulus clouds considered in the study, CDNC is overpredicted by 45% with the adiabatic parameterization. When entrainment is accounted for, the predicted CDNC agrees within 3.5%. Cloud‐averaged CDNC for stratocumulus clouds is well captured when entrainment is not considered. In all cases considered, the entraining parameterization compared favorably against a statistical correlation developed from observations to treat entrainment effects on droplet number. These results suggest that including entrainment effects in the calculation of CDNC, as presented here, could address important overprediction biases associated with using adiabatic CDNC to represent cloud‐scale average values

Thermodynamic characterization of Mexico City aerosol during MILAGRO 2006

Fast measurements of aerosol and gas-phase constituents coupled with the ISORROPIA-II thermodynamic equilibrium model are used to study the partitioning of semivolatile inorganic species and phase state of Mexico City aerosol sampled at the T1 site during the MILAGRO 2006 campaign. Overall, predicted semivolatile partitioning agrees well with measurements. PM<sub>2.5</sub> is insensitive to changes in ammonia but is to acidic semivolatile species. For particle sizes up to 1μm diameter, semi-volatile partitioning requires 15–30 min to equilibrate; longer time is typically required during the night and early morning hours. Aerosol and gas-phase speciation always exhibits substantial temporal variability, so that aerosol composition measurements (bulk or size-resolved) obtained over large integration periods are not reflective of its true state. When the aerosol sulfate-to-nitrate molar ratio is less than unity, predictions improve substantially if the aerosol is assumed to follow the deliquescent phase diagram. Treating crustal species as "equivalent sodium" (rather than explicitly) in the thermodynamic equilibrium calculations introduces important biases in predicted aerosol water uptake, nitrate and ammonium; neglecting crustals further increases errors dramatically. This suggests that explicitly considering crustals in the thermodynamic calculations is required to accurately predict the partitioning and phase state of aerosols

Optical-microphysical properties of Saharan dust aerosols and composition relationship using a multi-wavelength Raman lidar, in situ sensors and modelling: a case study analysis

A strong Saharan dust event that occurred over the city of Athens, Greece (37.9° N, 23.6° E) between 27 March and 3 April 2009 was followed by a synergy of three instruments: a 6-wavelength Raman lidar, a CIMEL sun-sky radiometer and the MODIS sensor. The BSC-DREAM model was used to forecast the dust event and to simulate the vertical profiles of the aerosol concentration. Due to mixture of dust particles with low clouds during most of the reported period, the dust event could be followed by the lidar only during the cloud-free day of 2 April 2009. The lidar data obtained were used to retrieve the vertical profile of the optical (extinction and backscatter coefficients) properties of aerosols in the troposphere. The aerosol optical depth (AOD) values derived from the CIMEL ranged from 0.33–0.91 (355 nm) to 0.18–0.60 (532 nm), while the lidar ratio (LR) values retrieved from the Raman lidar ranged within 75–100 sr (355 nm) and 45–75 sr (532 nm). Inside a selected dust layer region, between 1.8 and 3.5 km height, mean LR values were 83 ± 7 and 54 ± 7 sr, at 355 and 532 nm, respectively, while the Ångström-backscatter-related (ABR<sub>355/532</sub>) and Ångström-extinction-related (AER<sub>355/532</sub>) were found larger than 1 (1.17 ± 0.08 and 1.11 ± 0.02, respectively), indicating mixing of dust with other particles. Additionally, a retrieval technique representing dust as a mixture of spheres and spheroids was used to derive the mean aerosol microphysical properties (mean and effective radius, number, surface and volume density, and mean refractive index) inside the selected atmospheric layers. Thus, the mean value of the retrieved refractive index was found to be 1.49( ± 0.10) + 0.007( ± 0.007)i, and that of the effective radiuses was 0.30 ± 0.18 μm. The final data set of the aerosol optical and microphysical properties along with the water vapor profiles obtained by Raman lidar were incorporated into the ISORROPIA II model to provide a possible aerosol composition consistent with the retrieved refractive index values. Thus, the inferred chemical properties showed 12–40% of dust content, sulfate composition of 16–60%, and organic carbon content of 15–64%, indicating a possible mixing of dust with haze and smoke. PM<sub>10</sub> concentrations levels, PM<sub>10</sub> composition results and SEM-EDX (Scanning Electron Microscope-Energy Dispersive X-ray) analysis results on sizes and mineralogy of particles from samples during the Saharan dust transport event were used to evaluate the retrieval

Simulation of Cloud-aerosol Lidar with Orthogonal Polarization (CALIOP) attenuated backscatter profiles using the Global Model of Aerosol Processes (GLOMAP)

To permit the calculation of the radiative effects of atmospheric aerosols, we have linked our aerosol-chemical transport model (CTMGLOMAP) to a new radiation module (UKCARADAER). In order to help assess and improve the accuracy of the radiation code, in particular the height dependence of the predicted scattering, we have developed a module that simulates attenuated backscatter (ABS) profiles that would be measured by the satellite-borne Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) if it were to sample an atmosphere with the same aerosol loading as predicted by the CTM. Initial results of our comparisons of the predicted ABS profiles with actual CALIOP data are encouraging but some differences are noted, particularly in marine boundary layers where the scattering is currently under-predicted and in dust layers where it is often over-predicted. The sources of these differences are being investigated

Thermodynamic characterization of Mexico City aerosol during MILAGRO 2006

International audienceFast measurements of aerosol and gas-phase constituents coupled with the ISORROPIA-II thermodynamic equilibrium model are used to study the partitioning of semivolatile inorganic species and phase state of Mexico City aerosol sampled at the T1 site during the MILAGRO 2006 campaign. Overall, predicted semivolatile partitioning agrees well with measurements. PM2.5 is insensitive to changes in ammonia but is to acidic semivolatile species. Semi-volatile partitioning equilibrates on a timescale between 6 and 20 min. When the aerosol sulfate-to-nitrate molar ratio is less than 1, predictions improve substantially if the aerosol is assumed to follow the deliquescent phase diagram. Treating crustal species as "equivalent sodium" (rather than explicitly) in the thermodynamic equilibrium calculations introduces important biases in predicted aerosol water uptake, nitrate and ammonium; neglecting crustals further increases errors dramatically. This suggests that explicitly considering crustals in the thermodynamic calculations are required to accurately predict the partitioning and phase state of aerosols

Aerosol–cloud drop concentration closure for clouds sampled during the International Consortium for Atmospheric Research on Transport and Transformation 2004 campaign

This study analyzes 27 cumuliform and stratiform clouds sampled aboard the CIRPAS Twin Otter during the 2004 International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) experiment. The data set was used to assess cloud droplet closure using (1) a detailed adiabatic cloud parcel model and (2) a state-of-the-art cloud droplet activation parameterization. A unique feature of the data set is the sampling of highly polluted clouds within the vicinity of power plant plumes. Remarkable closure was achieved (much less than the 20% measurement uncertainty) for both parcel model and parameterization. The highly variable aerosol did not complicate the cloud droplet closure, since the clouds had low maximum supersaturation and were not sensitive to aerosol variations (which took place at small particle sizes). The error in predicted cloud droplet concentration was mostly sensitive to updraft velocity. Optimal closure is obtained if the water vapor uptake coefficient is equal to 0.06, but can range between 0.03 and 1.0. The sensitivity of cloud droplet prediction error to changes in the uptake coefficient, organic solubility and surface tension depression suggest that organics exhibit limited solubility. These findings can serve as much needed constraints in modeling of aerosol-cloud interactions in the North America; future in situ studies will determine the robustness of our findings

Evaluation of a three-dimensional chemical transport model (PMCAMx) in the European domain during the EUCAARI May 2008 campaign

PMCAMx-2008, a detailed three-dimensional chemical transport model (CTM), was applied to Europe to simulate the mass concentration and chemical composition of particulate matter (PM) during May 2008. The model includes a state-of-the-art organic aerosol module which is based on the volatility basis set framework treating both primary and secondary organic components as semivolatile and photochemically reactive. The model performance is evaluated against high time resolution aerosol mass spectrometer (AMS) ground and airborne measurements. Overall, organic aerosol is predicted to account for 32% of total PM<sub>1</sub> at ground level during May 2008, followed by sulfate (30%), crustal material and sea-salt (14%), ammonium (13%), nitrate (7%), and elemental carbon (4%). The model predicts that fresh primary OA (POA) is a small contributor to organic PM concentrations in Europe during late spring, and that oxygenated species (oxidized primary and biogenic secondary) dominate the ambient OA. The Mediterranean region is the only area in Europe where sulfate concentrations are predicted to be much higher than the OA, while organic matter is predicted to be the dominant PM<sub>1</sub> species in central and northern Europe. The comparison of the model predictions with the ground measurements in four measurement stations is encouraging. The model reproduces more than 94% of the daily averaged data and more than 87% of the hourly data within a factor of 2 for PM<sub>1</sub> OA. The model tends to predict relatively flat diurnal profiles for PM<sub>1</sub> OA in many areas, both rural and urban in agreement with the available measurements. The model performance against the high time resolution airborne measurements at multiple altitudes and locations is as good as its performance against the ground level hourly measurements. There is no evidence of missing sources of OA aloft over Europe during this period