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Submicron atmospheric aerosol samples were collected during the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) 2004 campaign on four platforms: Chebogue Point (Nova Scotia, Canada), Appledore Island (Maine), the CIRPAS Twin Otter over Ohio, and the NOAA R/V Ronald H. Brown in the Gulf of Maine. Saturated aliphatic C-C-H, unsaturated aliphatic C=C−H, aromatic C=C−H, organosulfur C-O-S, carbonyl C=O, and organic hydroxyl C-OH functional groups were measured by calibrated Fourier Transform Infrared (FTIR) spectroscopy at all four sampling platforms. The ratio of molar concentrations of carbonyl C=O to saturated aliphatic C-C-H groups was nearly constant at each sampling platform, with the Twin Otter samples having the lowest ratio at 0.1 and the three more coastal platforms having ratios of 0.4 and 0.5. Organic mass (OM) to organic carbon (OC) ratios follow similar trends for the four platforms, with the Twin Otter having the lowest ratio of 1.4 and the coastal platforms having slightly higher values typically between 1.5 and 1.6. Organosulfur compounds were occasionally observed. Collocated organic aerosol sampling with two Aerodyne aerosol mass spectrometers for OM, a Sunset Laboratory thermo-optical analysis instrument for OC, and an ion chromatography-particle into liquid sampler (IC-PILS) for speciated carboxylic acids provided comparable results for most of the project, tracking the time series of FTIR OM, OC, and carbonyl groups, respectively, and showing simultaneous peaks of similar magnitude during most of the project. The FTIR/IC-PILS comparison suggests that about 9% of the carbonyl groups found in submicron organic particles on the Twin Otter are typically associated with low molecular weight carboxylic acids.

Secondary organic aerosol (SOA) formation from the photooxidation of m-xylene, toluene, and benzene is investigated in the Caltech environmental chambers. Experiments are performed under two limiting NOx conditions; under high-NOx conditions the peroxy radicals (RO2) react only with NO, while under low-NOx conditions they react only with HO2. For all three aromatics studied (m-xylene, toluene, and benzene), the SOA yields (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) under low-NOx conditions substantially exceed those under high-NOx conditions, suggesting the importance of peroxy radical chemistry in SOA formation. Under low-NOx conditions, the SOA yields for m-xylene, toluene, and benzene are constant (36%, 30%, and 37%, respectively), indicating that the SOA formed is effectively nonvolatile under the range of Mo(>10 μg m−3) studied. Under high-NOx conditions, aerosol growth occurs essentially immediately, even when NO concentration is high. The SOA yield curves exhibit behavior similar to that observed by Odum et al. (1996, 1997a, b), although the values are somewhat higher than in the earlier study. The yields measured under high-NOx conditions are higher than previous measurements, suggesting a "rate effect" in SOA formation, in which SOA yields are higher when the oxidation rate is faster. Experiments carried out in the presence of acidic seed aerosol reveal no change of SOA yields from the aromatics as compared with those using neutral seed aerosol.

The CCN properties, surfactant characteristics, and droplet growth kinetics of secondary organic aerosol (SOA) formed from the ozonolysis of three parent alkene hydrocarbons (terpinolene, 1-methlycycloheptene and cycloheptene) are explored. Based on measurements of CCN activity, total carbon and inorganic ion concentrations, we estimate the average molar volume of the water-soluble organic component using Köhler Theory Analysis (KTA). The results suggest that the water-soluble organics in the SOA are composed of relatively low molecular weight species, with an effective molar mass less than 200 g mol?1. This finding is consistent with the speciated fraction for some of the SOA, and suggests that KTA can be applied to complex organic aerosol, such as that found in the atmosphere. From measurements of CCN activity and Köhler Theory, we apply a novel method to infer the surface tension at the point of activation; this is used to infer the presence of surface-active organics. It is found that the water-soluble carbon can be surface-active, depressing surface tension 10?15% from that of pure water at concentrations relevant for CCN activation. Although important, this level of surface tension depression is lower than expected for HULIS, which suggest that they are not likely in the SOA examined. In all cases, the CCN exhibit droplet growth kinetics similar to (NH4)2SO4.

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

International audience; We present the adjoint of the global chemical transport model GEOS-Chem, focusing on the chemical and thermodynamic relationships between sulfate ? ammonium ? nitrate aerosols and their gas-phase precursors. The adjoint model is constructed from a combination of manually and automatically derived discrete adjoint algorithms and numerical solutions to continuous adjoint equations. Explicit inclusion of the processes that govern secondary formation of inorganic aerosol is shown to afford efficient calculation of model sensitivities such as the dependence of sulfate and nitrate aerosol concentrations on emissions of SOx, NOx, and NH3. The accuracy of the adjoint model is extensively verified by comparing adjoint to finite difference sensitivities, which are shown to agree within acceptable tolerances. We explore the robustness of these results, noting how discontinuities in the advection routine hinder, but do not entirely preclude, the use of such comparisons for validation of the adjoint model. The potential for inverse modeling using the adjoint of GEOS-Chem is assessed in a data assimilation framework using simulated observations, demonstrating the feasibility of exploiting gas- and aerosol-phase measurements for optimizing emission inventories of aerosol precursors.

We present the adjoint of the global chemical transport model GEOS-Chem, focusing on the chemical and thermodynamic relationships between sulfate – ammonium – nitrate aerosols and their gas-phase precursors. The adjoint model is constructed from a combination of manually and automatically derived discrete adjoint algorithms and numerical solutions to continuous adjoint equations. Explicit inclusion of the processes that govern secondary formation of inorganic aerosol is shown to afford efficient calculation of model sensitivities such as the dependence of sulfate and nitrate aerosol concentrations on emissions of SOx, NOx, and NH3. The adjoint model is extensively validated by comparing adjoint to finite difference sensitivities, which are shown to agree within acceptable tolerances; most sets of comparisons have a nearly 1:1 correlation and R2>0.9. We explore the robustness of these results, noting how insufficient observations or nonlinearities in the advection routine can degrade the adjoint model performance. The potential for inverse modeling using the adjoint of GEOS-Chem is assessed in a data assimilation framework through a series of tests using simulated observations, demonstrating the feasibility of exploiting gas- and aerosol-phase measurements for optimizing emission inventories of aerosol precursors.

International audience; A variety of thermodynamic models have been developed to predict inorganic gas-aerosol equilibrium. To achieve computational efficiency a number of the models rely on a priori specification of the phases present in certain relative humidity regimes. Presented here is a new computational model, named UHAERO, that is both efficient and rigorously computes phase behavior without any a priori specification. The computational implementation is based on minimization of the Gibbs free energy using a primal-dual method, coupled to a Newton iteration. The mathematical details of the solution are given elsewhere. The model also computes deliquescence and crystallization behavior without any a priori specification of the relative humidities of deliquescence or crystallization. Detailed phase diagrams of the sulfate/nitrate/ammonium/water system are presented as a function of relative humidity at 298.15 K over the complete space of composition.

Our understanding of the activation of aerosol particles into cloud drops during the formation of warm cumulus clouds presently has a limited observational foundation. Detailed observations of aerosol size and composition, cloud microphysics and dynamics, and atmospheric thermodynamic state were collected in a systematic study of 21 cumulus clouds by the Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter aircraft during NASA's Cirrus Regional Study of Tropical Anvils and Cirrus Layers–Florida Area Cirrus Experiment (CRYSTAL-FACE). An “aerosol-cloud” closure study was carried out in which a detailed cloud activation parcel model, which predicts cloud drop concentration using observed aerosol concentration, size distribution, cloud updraft velocity, and thermodynamic state, is evaluated against observations. On average, measured droplet concentration in adiabatic cloud regions is within 15% of the predictions. This agreement is corroborated by independent measurements of aerosol activation carried out by two cloud condensation nucleus (CCN) counters on the aircraft. Variations in aerosol concentration, which ranged from 300 to 3300 cm^(−3), drives large microphysical differences (250–2300 cm^(−3)) observed among continental and maritime clouds in the South Florida region. This is the first known study in which a cloud parcel model is evaluated in a closure study using a constraining set of data collected from a single platform. Likewise, this is the first known study in which relationships among aerosol size distribution, CCN spectrum, and cloud droplet concentration are all found to be consistent with theory within experimental uncertainties much less than 50%. Vertical profiles of cloud microphysical properties (effective radius, droplet concentration, dispersion) clearly demonstrate the boundary layer aerosol's effect on cloud microphysics throughout the lowest 1 km of cloud depth. Onboard measurements of aerosol hygroscopic growth and the organic to sulfate mass ratio are related to CCN properties. These chemical data are used to quantify the range of uncertainty associated with the simplified treatment of aerosol composition assumed in the closure study.

Estimates of indirect aerosol radiative forcing have focused on increased sulfate aerosol mass concentrations caused by anthropogenic emissions of gas-phase sulfur dioxide, implicitly neglecting the impact of direct particulate emissions. Emissions of primary particles and gas-phase precursors have different effects on cloud condensation nuclei (CCN) concentrations as they impact CCN concentrations via different microphysical pathways. We present a theoretical analysis and evidence from a three-dimensional global model of aerosol microphysics to show that particulate emissions are more efficient per unit mass than gas-phase emissions at increasing CCN concentrations. Both analyses show that the few percent of anthropogenic sulfur emitted as particulate sulfate results in an increase in CCN concentrations comparable to that resulting from much larger emissions of gas-phase sulfur dioxide. Therefore, models should explicitly distinguish between the microphysical impacts of particulate and gas-phase emissions to accurately estimate the magnitude of the indirect effect of aerosols on climate.

We will present an overview of early airborne results obtained aboard the Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRP AS) Twin Otter aircraft during the Atmospheric Radiation Measurement (ARM) program aerosol intensive observation period in May 2003.

From March to May 2001, aerosol size distributions and chemical compositions were measured using differential mobility analyzers (DMA), an aerodynamic particle sizer (APS), Micro-Orifice Uniform Deposit Impactors (MOUDI), and denuder samplers onboard the Twin Otter aircraft as part of the Aerosol Characterization Experiment (ACE)-Asia campaign. Of the 19 research flights, measurements on four flights that represented different aerosol characteristics are analyzed in detail. Clear-column radiative closure is studied by comparing aerosol extinctions predicted using in situ aerosol size distribution and chemical composition measurements to those derived from the 14-wavelength NASA Ames Airborne Tracking Sun photometer (AATS-14). In the boundary layer, pollution layers, and free troposphere with no significant mineral dust present, aerosol extinction closure was achieved within the estimated uncertainties over the full range of wavelengths of AATS-14. Aerosol extinctions predicted based on measured size distributions also reproduce the wavelength dependence derived from AATS-14 data. Considering all four flights, the best fit lines yield Predicted/Observed ratios in boundary and pollution layers of 0.97 ± 0.24 and 1.07 ± 0.08 at λ = 525 nm and 0.96 ± 0.21 and 1.08 ± 0.08 at λ = 1059 nm, respectively. In free troposphere dust layers, aerosol extinctions predicted from the measured size distributions were generally smaller than those derived from the AATS-14 data, with Predicted/Observed ratios of 0.65 ± 0.06 and 0.66 ± 0.05 at 525 and 1059 nm, respectively. A detailed analysis suggests that the discrepancy is likely a result of the lack of the knowledge of mineral dust shape as well as variations in aerosol extinction derived from AATS-14 data when viewing through horizontally inhomogeneous layers.

The North Atlantic Regional Aerosol Characterization Experiment (ACE-2) of the International Global Atmospheric Chemistry Project (IGAC) ran from 16 June to 25 July 1997. The results presented in this study are part of the "Clear-sky column closure experiment" (CLEARCOLUMN) activity, one of 6 ACE-2 activities [1]. Clear-sky column closure experiments call for characterization of aerosol layers by simultaneous measurements using different techniques that can be related using models [2]. A wide range of aerosol types was encountered throughout the ACE-2 area, including background Atlantic marine, European pollution-derived and African mineral dust. In a series of papers, we reported on ACE-2 CLEARCOLUMN results obtained by combining airborne sunphotometer and in-situ measurements taken aboard the Pelican aircraft, spaceborne NOAA/VHRR data and ground-based lidar and sunphotometer measurements [3]-[10]. Those and other CLEARCOLUMN results have been summarized in [11]. In this paper we only report on results not shown in this form in [3]-[11].

In spring 2001 the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) made extensive measurements from land, ocean, air and space platforms. A primary objective was to quantify the interactions between aerosols and radiation. This talk presents illustrative results from each type of platform, with initial assessments of regional aerosol radiative forcing obtained by combining satellite and suborbital results.

An increase in cloud droplet number concentration resulting from an increase in ambient aerosol (and subsequent albedo increase) is typically identified as the first indirect (or ‘‘Twomey’’) climatic effect of aerosols [Twomey, 1974]. A key question is whether chemical effects (dissolution of soluble gases and slightly soluble substances, surface tension depression by organic substances and accommodation coefficient changes) could potentially rival changes in droplet number from changes in aerosol number concentration. We assess the sensitivity of cloud droplet number concentration to such chemical factors, using a cloud parcel model. We find that numerous conditions exist, for which chemical influences on cloud droplet activation can indeed rival the Twomey effect.

A classical theory of the ternary homogeneous nucleation of sulfuric acid—ammonia—water is presented. For NH3 mixing ratios exceeding 1 ppt, the presence of ammonia enhances the binary (sulfuric acid—water) nucleation rate by several orders of magnitude. However, the limiting component for ternary nucleation—as for binary nucleation—is sulfuric acid. The sulfuric acid concentration needed for significant ternary nucleation is several orders of magnitude below that required in binary case.