ABSTRACT
Acidity, defined as pH, is a central component of aqueous chemistry. In the atmosphere, the acidity of condensed phases (aerosol particles, cloud water, and fog droplets) governs the phase partitioning of semi-volatile gases such as HNO3, NH3, HCl, and organic acids and bases as well as chemical reaction rates. It has implications for the atmospheric lifetime of pollutants, deposition, and human health. Despite its fundamental role in atmospheric processes, only recently has this field seen a growth in the number of studies on particle acidity. Even with this growth, many fine particle pH estimates must be based on thermodynamic model calculations since no operational techniques exist for direct measurements. Current information indicates acidic fine particles are ubiquitous, but observationally-constrained pH estimates are limited in spatial and temporal coverage. Clouds and fogs are also generally acidic, but to a lesser degree than particles, and have a range of pH that is quite sensitive to anthropogenic emissions of sulfur and nitrogen oxides, as well as ambient ammonia. Historical measurements indicate that cloud and fog droplet pH has changed in recent decades in response to controls on anthropogenic emissions, while the limited trend data for aerosol particles indicates acidity may be relatively constant due to the semi-volatile nature of the key acids and bases and buffering in particles. This paper reviews and synthesizes the current state of knowledge on the acidity of atmospheric condensed phases, specifically particles and cloud droplets. It includes recommendations for estimating acidity and pH, standard nomenclature, a synthesis of current pH estimates based on observations, and new model calculations on the local and global scale.
ABSTRACT
Atmospheric aerosol particles (especially particles with aerodynamic diameters equal to or less than 2.5 µm, called PM2.5) can affect the surface energy balance and atmospheric heating rates and thus may impact the intensity of urban heat islands. In this paper, the effect of fine particles on the urban heat island intensity in Nanjing was investigated via the analysis of observational data and numerical modelling. The observations showed that higher PM2.5 concentrations over the urban area corresponded to lower urban heat island (UHI) intensities, especially during the day. Under heavily polluted conditions, the UHI intensity was reduced by up to 1 K. The numerical simulation results confirmed the weakening of the UHI intensity due to PM2.5 via the higher PM2.5 concentrations present in the urban region than those in the suburban areas. The effects of the fine particles on the UHI reduction were limited to the lowest 500-1000 m. The daily range of the surface air temperature was also reduced by up to 1.1 K due to the particles' radiative effects. In summary, PM2.5 noticeably impacts UHI intensity, which should be considered in future studies on air pollution and urban climates.
ABSTRACT
Atmospheric black carbon (BC) exerts a strong, but uncertain, warming effect on the climate. BC that is coated with non-absorbing material absorbs more strongly than the same amount of BC in an uncoated particle, but the magnitude of this absorption enhancement (Eabs) is not well constrained. Modelling studies and laboratory measurements have found stronger absorption enhancement than has been observed in the atmosphere. Here, using a particle-resolved aerosol model to simulate diverse BC populations, we show that absorption is overestimated by as much as a factor of two if diversity is neglected and population-averaged composition is assumed across all BC-containing particles. If, instead, composition diversity is resolved, we find Eabs=1-1.5 at low relative humidity, consistent with ambient observations. This study offers not only an explanation for the discrepancy between modelled and observed absorption enhancement, but also demonstrates how particle-scale simulations can be used to develop relationships for global-scale models.
