Relation of emissions to air quality for photochemical smog

Effective evaluation of air pollution control strategies requires the use of validated and reliable mathemtical models that can relate pollutant emissions to atmospheric air quality. The primary objective of this research program has been to develop a fundamental capability to assess the effectiveness of air pollution control measures in reducing photochemical air pollution. An important aspect of the development has been to simplify the preparation of input data and operational use of the resulting model. The system has been designed to be used by air pollution agencies with relatively little experience in atmospheric physics and chemistry. The assumptions commonly employed in model formulations have been evaluated to ensure a valid representation of the physical and chemical processes in the atmosphere. In the most recent phase of this research the comprehensive photochemical airshed model has been evaluated against data available in the South Coast Air Basin of Southern California. This task was undertaken in collaboration with the California Air Resources Board, Air Quality Modeling Section. A statistical analysis package has been used to evaluate the correspondence of predicted and observed concentrations for the days on which the model was evaluated. An assessment of the EPA ozone isopleth modeling technique has been initiated

A differentiable trajectory approximation to turbulent diffusion

The problem of turbulent diffusion is posed as determining the time evolution of the probability density of the concentration given those for the fluid velocity components, sources, and the initial concentration. At each time, all variables are elements of the Hilbert space L^2_R(R^3), and a finite-dimensional approximation based on expansions in orthonormal basis functions is developed. An expression for the joint probability density of all the Fourier coefficients is derived, the evaluation of which is shown to be particularly straightforward. Diffusion of material from a single source in an unbounded mildly turbulent fluid is considered as an application

Effect of cluster scavenging on homogeneous nucleation

A closed‐form expression for the effect of cluster scavenging on the rate of homogeneous nucleation of a vapor in the presence of continuum regime particles is obtained by solving the kinetic equation of nucleation by the method of singular perturbation. The reduction in nucleation rate of a condensing species at a given supersaturation is shown to be dependent largely on the number concentration, the size of the sink particles, and the molecular number concentration of the background gas. The reduction in the rate of nucleation due to the cluster scavenging by transition regime particles is also discussed

Modeling the gas-particle partitioning of secondary organic aerosol: the importance of liquid-liquid phase separation

The partitioning of semivolatile organic compounds between the gas phase and aerosol particles is an important source of secondary organic aerosol (SOA). Gas-particle partitioning of organic and inorganic species is influenced by the physical state and water content of aerosols, and therefore ambient relative humidity (RH), as well as temperature and organic loading levels. We introduce a novel combination of the thermodynamic models AIOMFAC (for liquid mixture non-ideality) and EVAPORATION (for pure compound vapor pressures) with oxidation product information from the Master Chemical Mechanism (MCM) for the computation of gas-particle partitioning of organic compounds and water. The presence and impact of a liquid-liquid phase separation in the condensed phase is calculated as a function of variations in relative humidity, organic loading levels, and associated changes in aerosol composition. We show that a complex system of water, ammonium sulfate, and SOA from the ozonolysis of α-pinene exhibits liquid-liquid phase separation over a wide range of relative humidities (simulated from 30% to 99% RH). Since fully coupled phase separation and gas-particle partitioning calculations are computationally expensive, several simplified model approaches are tested with regard to computational costs and accuracy of predictions compared to the benchmark calculation. It is shown that forcing a liquid one-phase aerosol with or without consideration of non-ideal mixing bears the potential for vastly incorrect partitioning predictions. Assuming an ideal mixture leads to substantial overestimation of the particulate organic mass, by more than 100% at RH values of 80% and by more than 200% at RH values of 95%. Moreover, the simplified one-phase cases stress two key points for accurate gas-particle partitioning calculations: (1) non-ideality in the condensed phase needs to be considered and (2) liquid-liquid phase separation is a consequence of considerable deviations from ideal mixing in solutions containing inorganic ions and organics that cannot be ignored. Computationally much more efficient calculations relying on the assumption of a complete organic/electrolyte phase separation below a certain RH successfully reproduce gas-particle partitioning in systems in which the average oxygen-to-carbon (O:C) ratio is lower than ~0.6, as in the case of α-pinene SOA, and bear the potential for implementation in atmospheric chemical transport models and chemistry-climate models. A full equilibrium calculation is the method of choice for accurate offline (box model) computations, where high computational costs are acceptable. Such a calculation enables the most detailed predictions of phase compositions and provides necessary information on whether assuming a complete organic/electrolyte phase separation is a good approximation for a given aerosol system. Based on the group-contribution concept of AIOMFAC and O:C ratios as a proxy for polarity and hygroscopicity of organic mixtures, the results from the α-pinene system are also discussed from a more general point of view

Aerosol-cloud interactions in global models of indirect aerosol radiative forcing

The sensitivity of cloud optical properties with respect to parameters that affect aerosol activation is examined. Of particular interest are the effect of volatile gases (such as HNO3), slightly soluble and surfactant species. An adiabatic parcel model is used to simulate cloud droplet formation. Cloud optical properties are calculated from these simulations

Organic atmospheric particulate material

Carbonaceous compounds comprise a substantial fraction of atmospheric particulate matter (PM). Particulate organic material can be emitted directly into the atmosphere or formed in the atmosphere when the oxidation products of certain volatile organic compounds condense. Such products have lower volatilities than their parent molecules as a result of the fact that adding oxygen and/or nitrogen to organic molecules reduces volatility. Formation of secondary organic PM is often described in terms of a fractional mass yield, which relates how much PM is produced when a certain amount of a parent gaseous organic is oxidized. The theory of secondary organic PM formation is outlined, including the role of water, which is ubiquitous in the atmosphere. Available experimental studies on secondary organic PM formation and molecular products are summarized

Development of the adjoint of GEOS-Chem

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

Study of the Aerosol Indirect Effect by Large-Eddy Simulation of Marine Stratocumulus

A total of 98 three-dimensional large-eddy simulations (LESs) of marine stratocumulus clouds covering both nighttime and daytime conditions were performed to explore the response of cloud optical depth (τ) to various aerosol number concentrations (Na = 50–2500 cm−3) and the covarying meteorological conditions (large-scale divergence rate and SST). The idealized First International Satellite Cloud Climatology Project (ISCCP) Regional Experiment (FIRE) and the Atlantic Stratocumulus Transition Experiment (ASTEX) Lagrangian 1 sounding profiles were used to represent the lightly and heavily drizzling cases, respectively. The first and second aerosol indirect effects are identified. Through statistical analysis, τ is found be to both positively correlated with Na and cloud liquid water path (LWP) with a higher correlation associated with LWP, which is predominantly regulated by large-scale subsidence and SST. Clouds with high LWP occur under low SST or weak large-scale subsidence. Introduction of a small amount of giant sea salt aerosol into the simulation lowers the number of cloud droplets activated, results in larger cloud droplets, and initiates precipitation for nondrizzling polluted clouds or precedes the precipitation process for drizzling clouds. However, giant sea salt aerosol is found to have a negligible effect on τ for lightly precipitating cases, while resulting in a relative reduction of τ of 3%–77% (increasing with Na, for Na = 1000–2500 cm−3) for heavily precipitating cases, suggesting that the impact of giant sea salt is only important for moist and potentially convective clouds. Finally, a regression analysis of the simulations shows that the second indirect effect is more evident in clear than polluted cases. The second indirect effect is found to enhance (reduce) the overall aerosol indirect effect for heavily (lightly) drizzling clouds; that is, τ is larger (smaller) for the same relative change in Na than considering the Twomey (first indirect) effect alone. The aerosol indirect effect (on τ) is lessened in the daytime afternoon conditions and is dominated by the Twomey effect; however, the effect in the early morning is close but slightly smaller than that in the nocturnal run. Diurnal variations of the aerosol indirect effect should be considered to accurately assess its magnitude

Nonisothermal homogeneous nucleation

Classical homogeneous nucleation theory is extended to nonisothermal conditions through simultaneous cluster mass and energy balances. The transient nucleation of water vapor following a sudden increase in saturation ratio is studied by numerically solving the coupled mass and energy balance equations. The ultimate steady state nucleation rate, considering nonisothermal effects, is found to be lower than the corresponding isothermal rate, with the discrepancy increasing as the pressure of the background gas decreases. After the decay of the initial temperature transients, subcritical clusters in the vicinity of the critical cluster are found to have temperatures elevated with respect to that of the background gas