Formation and growth rates of ultrafine atmospheric particles: a review of observations

Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar radiation and by acting as cloud condensation nuclei. The quantitative assessment of such climate effects remains hampered by a number of factors, including an incomplete understanding of how biogenic VOCs contribute to the formation of atmospheric secondary organic aerosol. The growth of newly formed particles from sizes of less than three nanometres up to the sizes of cloud condensation nuclei (about one hundred nanometres) in many continental ecosystems requires abundant, essentially non-volatile organic vapours, but the sources and compositions of such vapours remain unknown. Here we investigate the oxidation of VOCs, in particular the terpene α-pinene, under atmospherically relevant conditions in chamber experiments. We find that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours. These vapours form at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally.

A large source of low-volatility secondary organic aerosol

Nucleation and Growth of Nanoparticles in the Atmosphere Renyi Zhang,* Alexei Khalizov, Lin Wang, Min Hu, and Wen Xu Department of Atmospheric Sciences andDepartment of Chemistry, Center for Atmospheric Chemistry and Environment, Texas A&M University, College Station, Texas 77843, United States Department of Environmental Science & Engineering and Institute of Global Environment Change Research, Fudan University, Shanghai 200433, China State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, China

Nucleation and Growth of Nanoparticles in the Atmosphere

Atmospheric nucleation is the dominant source of aerosol particles in the global atmosphere and an important player in aerosol climatic effects. The key steps of this process occur in the sub–2-nanometer (nm) size range, in which direct size-segregated observations have not been possible until very recently. Here, we present detailed observations of atmospheric nanoparticles and clusters down to 1-nm mobility diameter. We identified three separate size regimes below 2-nm diameter that build up a physically, chemically, and dynamically consistent framework on atmospheric nucleation—more specifically, aerosol formation via neutral pathways. Our findings emphasize the important role of organic compounds in atmospheric aerosol formation, subsequent aerosol growth, radiative forcing and associated feedbacks between biogenic emissions, clouds, and climate.

http://science.sciencemag.org/content/sci/339/6122/943.full.pdf

Direct observations of atmospheric aerosol nucleation.

Nucleation is a fundamental step in atmospheric new-particle formation. However, laboratory experiments on nucleation have systematically failed to demonstrate sulfuric acid particle formation rates as high as those necessary to account for ambient atmospheric concentrations, and the role of sulfuric acid in atmospheric nucleation has remained a mystery. Here, we report measurements of new particles (with diameters of approximately 1.5 nanometers) observed immediately after their formation at atmospherically relevant sulfuric acid concentrations. Furthermore, we show that correlations between measured nucleation rates and sulfuric acid concentrations suggest that freshly formed particles contain one to two sulfuric acid molecules, a number consistent with assumptions that are based on atmospheric observations. Incorporation of these findings into global models should improve the understanding of the impact of secondary particle formation on climate.

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The Role of Sulfuric Acid in Atmospheric Nucleation

Measurements of gas phase sulfuric and methane sulfonic acid (MSA) have been performed using a relatively new atmospheric pressure selected ion chemical ionization mass spectrometric technique at two field sites. Both gas phase acids are photooxidation products, and their concentrations are seen to qualitatively follow solar flux. While sulfuric acid concentrations typically decline in conjunction with declining solar radiation, they sometimes level off in the mid 105–106 molecules cm−3 range after dark, even in relatively clean air. The reason for this quasi-stable nighttime sulfuric acid concentration is not well understood but may be a result of a steady state exchange of sulfuric acid between particles and the gas phase.

Measurements of OH, H2SO4, and SO2 concentrations in conjunction with aerosol number and size distribution also made possible the independent calculation of gas phase sulfuric acid production and loss rates. Calculated production and loss rates are seen to agree well in relatively clean air during the daylight hours. At night, however, the sulfuric acid concentrations and its calculated loss rate often have a nonzero value. In more polluted air masses, calculated gas phase sulfuric acid losses significantly exceed calculated production if H2SO4/aerosol reaction probabilities of 1.0 or 0.5 are assumed.

F. L. Eisele

Papers

Measurement of the gas phase concentration of H2SO4 and methane sulfonic acid and estimates of H2SO4 production and loss in the atmosphere