CCN activity and droplet growth kinetics of fresh and aged monoterpene secondary organic aerosol

International audienceThe ability of secondary organic aerosol (SOA) produced from the ozonolysis of ?-pinene and monoterpene mixtures (?-pinene, ?-pinene, limonene and 3-carene) to become cloud droplets was investigated. Monoterpene SOA is quite active and would likely be a good source of cloud condensation nuclei (CCN) in the atmosphere. A static CCN counter and a Scanning Mobility CCN Analyser (a Scanning Mobility Particle Sizer coupled with a Continuous Flow counter) were used for the CCN measurements. A decrease in CCN activation diameter for ?-pinene SOA of approximately 3 nm h?1 was observed as the aerosol continued to react with oxidants. Hydroxyl radicals further oxidize the SOA particles thereby enhancing the particle CCN activity with time. The initial concentrations of ozone and monoterpene precursor (for concentrations lower than 40 ppb) do not appear to affect the activity of the resulting SOA. Köhler Theory Analysis (KTA) is used to infer the molar mass of the SOA sampled online and offline from atomized filter samples. KTA suggests that the aged aerosol (both from ?-pinene and the mixed monoterpene oxidation) is primarily water-soluble (around 70?80%), with an estimated average molar mass of 180±55 g mol?1 (consistent with existing SOA speciation studies). CCN activity measurements of the SOA mixed with (NH4)2SO4 suggest that the organic can depress surface tension by as much as 10 nM m?1 (with respect to pure water). The droplet growth kinetics of SOA samples are similar to (NH4)2SO4, except at low supersaturation, where SOA tends to grow more slowly. The CCN activity of ?-pinene and mixed monoterpene SOA can be modelled by a very simple implementation of Köhler theory, assuming complete dissolution of the particles, no dissociation into ions, molecular weight of 180 g mol?1, density of 1.5 g cm?3, and surface tension to within 10?15% of water

Adjoint sensitivity of global cloud droplet number to aerosol and dynamical parameters

We present the development of the adjoint of a comprehensive cloud droplet formation parameterization for use in aerosol-cloud-climate interaction studies. The adjoint efficiently and accurately calculates the sensitivity of cloud droplet number concentration (CDNC) to all parameterization inputs (e.g., updraft velocity, water uptake coefficient, aerosol number and hygroscopicity) with a single execution. The adjoint is then integrated within three dimensional (3-D) aerosol modeling frameworks to quantify the sensitivity of CDNC formation globally to each parameter. Sensitivities are computed for year-long executions of the NASA Global Modeling Initiative (GMI) Chemical Transport Model (CTM), using wind fields computed with the Goddard Institute for Space Studies (GISS) Global Circulation Model (GCM) II', and the GEOS-Chem CTM, driven by meteorological input from the Goddard Earth Observing System (GEOS) of the NASA Global Modeling and Assimilation Office (GMAO). We find that over polluted (pristine) areas, CDNC is more sensitive to updraft velocity and uptake coefficient (aerosol number and hygroscopicity). Over the oceans of the Northern Hemisphere, addition of anthropogenic or biomass burning aerosol is predicted to increase CDNC in contrast to coarse-mode sea salt which tends to decrease CDNC. Over the Southern Oceans, CDNC is most sensitive to sea salt, which is the main aerosol component of the region. Globally, CDNC is predicted to be less sensitive to changes in the hygroscopicity of the aerosols than in their concentration with the exception of dust where CDNC is very sensitive to particle hydrophilicity over arid areas. Regionally, the sensitivities differ considerably between the two frameworks and quantitatively reveal why the models differ considerably in their indirect forcing estimates

Inorganic salts interact with organic di-acids in sub-micron particles to form material with low hygroscopicity and volatility.

Volatility and hygroscopicity are two key properties of organic aerosol components, and both are strongly related to chemical identity. Here we show that inorganic-organic component interactions typically not considered in atmospheric models may strongly affect aerosol volatility and hygroscopicity. In particular, bi-dentate binding of di-carboxylic acids (DCA) to soluble inorganic ions can lead to very strongly bound metal-organic complexes with largely undetermined hygroscopicity and volatility. These reactions profoundly impact particle hygroscopicity, transforming hygroscopic components into irreversibly non-hygroscopic material. While the hygroscopicities of pure salts, DCA, and DCA salts are known, the hygroscopicity of internal mixtures of hygroscopic salts and DCA, as they are typically found in the atmosphere, has not been fully characterized. We have studied the volatility of pure, dry organic salt particles and the hygroscopicity of internal mixtures of oxalic acid (OxA, the dominant DCA in the atmosphere) and a number of salts, both mono- and di-valent. The formation of very low volatility organic salts was confirmed, with minimal evaporation of oxalate salt particles below 75 C. Dramatic increases in the CCN activation diameter for particles with divalent salts (e.g. CaCl2) and relatively small particle mass fractions of OxA indicate that standard volume additivity rules for hygroscopicity do not apply. Thus small organic compounds with high O : C are capable of forming low volatility and very low hygroscopicity particles. Given current knowledge of the formation mechanisms of OxA and M-Ox salts, surface enrichment of insoluble M-Ox salts is expected. The resulting formation of an insoluble coating of metal-oxalate salts can explain low particle hygroscopicities. The formation of particles with a hard coating could offer an alternative explanation for observations of glass-like particles with very low viscosity

Climatic effects of 1950-2050 changes in US anthropogenic aerosols - Part 2: Climate response

We investigate the climate response to changing US anthropogenic aerosol sources over the 1950–2050 period by using the NASA GISS general circulation model (GCM) and comparing to observed US temperature trends. Time-dependent aerosol distributions are generated from the GEOS-Chem chemical transport model applied to historical emission inventories and future projections. Radiative forcing from US anthropogenic aerosols peaked in 1970–1990 and has strongly declined since due to air quality regulations. We find that the regional radiative forcing from US anthropogenic aerosols elicits a strong regional climate response, cooling the central and eastern US by 0.5–1.0 °C on average during 1970–1990, with the strongest effects on maximum daytime temperatures in summer and autumn. Aerosol cooling reflects comparable contributions from direct and indirect (cloud-mediated) radiative effects. Absorbing aerosol (mainly black carbon) has negligible warming effect. Aerosol cooling reduces surface evaporation and thus decreases precipitation along the US east coast, but also increases the southerly flow of moisture from the Gulf of Mexico resulting in increased cloud cover and precipitation in the central US. Observations over the eastern US show a lack of warming in 1960–1980 followed by very rapid warming since, which we reproduce in the GCM and attribute to trends in US anthropogenic aerosol sources. Present US aerosol concentrations are sufficiently low that future air quality improvements are projected to cause little further warming in the US (0.1 °C over 2010–2050). We find that most of the warming from aerosol source controls in the US has already been realized over the 1980–2010 period

Profiling aerosol optical, microphysical and hygroscopic properties in ambient conditions by combining in situ and remote sensing

We present the In situ/Remote sensing aerosol Retrieval Algorithm (IRRA) that combines airborne in situ and lidar remote sensing data to retrieve vertical profiles of ambient aerosol optical, microphysical and hygroscopic properties, employing the ISORROPIA II model for acquiring the particle hygroscopic growth. Here we apply the algorithm on data collected from the Facility for Airborne Atmospheric Measurements (FAAM) BAe-146 research aircraft during the ACEMED campaign in the Eastern Mediterranean. Vertical profiles of aerosol microphysical properties have been derived successfully for an aged smoke plume near the city of Thessaloniki with aerosol optical depth of ∼0.4 at 532 nm, single scattering albedos of ∼0.9-0.95 at 550 nm and typical lidar ratios for smoke of ∼60-80 sr at 532 nm. IRRA retrieves highly hydrated particles above land, with 55 and 80% water volume content for ambient relative humidity of 80 and 90%, respectively. The proposed methodology is highly advantageous for aerosol characterization in humid conditions and can find valuable applications in aerosol-cloud interaction schemes. Moreover, it can be used for the validation of active space-borne sensors, as is demonstrated here for the case of CALIPSO

Relating CCN activity, volatility, and droplet growth kinetics of ?-caryophyllene secondary organic aerosol

International audienceThis study investigates the droplet formation characteristics of secondary organic aerosol (SOA) formed during the ozonolysis of sesquiterpene ?-caryophyllene (with and without hydroxyl radicals present). Emphasis is placed on understanding the role of semi-volatile material on Cloud Condensation Nucleus (CCN) activity and droplet growth kinetics. Aging of ?-caryophyllene SOA significantly affects all CCN-relevant properties measured throughout the experiments. Using a thermodenuder and two CCN instruments, we find that CCN activity is a strong function of temperature (activation diameter at ~0.6% supersaturation: 100±10 nm at 20°C and 130±10 nm at 35°C), suggesting that the hygroscopic fraction of the SOA is volatile. The water-soluble organic carbon (WSOC) is extracted from the SOA and characterized with Köhler Theory Analysis (KTA); the results suggest that the WSOC is composed of low molecular weight (?1) slightly surface-active material that constitute 5?15% of the SOA mass. These properties are similar to the water-soluble fraction of monoterpene SOA, suggesting that predictive understanding of SOA CCN activity requires knowledge of the WSOC fraction but not its exact speciation. Droplet growth kinetics of the CCN are found to be strongly anticorrelated with WSOC fraction, suggesting that the insoluble material in the SOA forms a kinetic barrier that delays droplet growth. These results have important implications for the droplet formation characteristics of SOA, and the atmospheric relevance of CCN measurements carried out at temperatures different from ambient

On the representation of droplet coalescence and autoconversion: evaluation using ambient cloud droplet size distributions

In this study, we evaluate eight autoconversion parameterizations against integration of the Kinetic Collection Equation (KCE) for cloud size distributions measured during the NASA CRYSTAL‐FACE and CSTRIPE campaigns. KCE calculations are done using both the observed data and fits of these data to a gamma distribution function; it is found that the fitted distributions provide a good approximation for calculations of total coalescence but not for autoconversion because of fitting errors near the drop‐drizzle separation size. Parameterizations that explicitly compute autoconversion tend to be in better agreement with KCE but are subject to substantial uncertainty, about an order of magnitude in autoconversion rate. Including turbulence effects on droplet collection increases autoconversion by a factor of 1.82 and 1.24 for CRYSTAL‐FACE and CSTRIPE clouds, respectively; this enhancement never exceeds a factor of 3, even under the most aggressive collection conditions. Shifting the droplet‐drizzle separation radius from 20 to 25 μm results in about a twofold uncertainty in autoconversion rate. The polynomial approximation to the gravitation collection kernel used to develop parameterizations provides computation of autoconversion that agree to within 30%. Collectively, these uncertainties have an important impact on autoconversion but are all within the factor of 10 uncertainty of autoconversion parameterizations. Incorporating KCE calculations in GCM simulations of aerosol‐cloud interactions studies is computationally feasible by using precalculated collection kernel tables and can quantify the autoconversion uncertainty associated with application of parameterizations

On the implications of aerosol liquid water and phase separation for modeled organic aerosol mass

Water is an important component of PM2.5 Many traditional SOA species are highly soluble and thus can be considered extractable Water can influence the partitioning of compounds traditionally considered insoluble in models Organic aerosol takes up water according to RH Organic aerosol interacts with inorganic water Deviations in ideality (solubility) must be considered

Downscaling a Global Climate Model to Simulate Climate Change Impacts on U.S. Regional and Urban Air Quality

Climate change can exacerbate future regional air pollution events by making conditions more favorable to form high levels of ozone. In this study, we use spectral nudging with WRF to downscale NASA earth system GISS modelE2 results during the years 2006 to 2010 and 2048 to 2052 over the continental United States in order to compare the resulting meteorological fields from the air quality perspective during the four seasons of five-year historic and future climatological periods. GISS results are used as initial and boundary conditions by the WRF RCM to produce hourly meteorological fields. The downscaling technique and choice of physics parameterizations used are evaluated by comparing them with in situ observations. This study investigates changes of similar regional climate conditions down to a 12km by 12km resolution, as well as the effect of evolving climate conditions on the air quality at major U.S. cities. The high resolution simulations produce somewhat different results than the coarse resolution simulations in some regions. Also, through the analysis of the meteorological variables that most strongly influence air quality, we find consistent changes in regional climate that would enhance ozone levels in four regions of the U.S. during fall (Western U.S., Texas, Northeastern, and Southeastern U.S), one region during summer (Texas), and one region where changes potentially would lead to better air quality during spring (Northeast). We also find that daily peak temperatures tend to increase in most major cities in the U.S. which would increase the risk of health problems associated with heat stress. Future work will address a more comprehensive assessment of emissions and chemistry involved in the formation and removal of air pollutants

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