Nucleation and Growth of Atmospheric Particles

New particle formation (NPF) in the atmospheric is a two-step process: Nucleation leads to the birth of stable nuclei that subsequently grow to sizes that can be detected and affect the atmosphere’s radiative properties. Our group is studying both of these processes. Our nucleation research is largely supported by NSF and involves measurements of neutral molecular clusters formed by nucleation with a new custom-designed mass spectrometer (the Cluster-CIMS) and measurements of nanoparticle size distributions as small as 1 nm with a new aerosol spectrometer (the DEG SMPS). These measurements are providing new insights into aspects of cluster behavior that affect nucleation rates. The U.S. DOE supports our research on nanoparticle growth rates. This research couples physical and chemical measurements of aerosol properties and behavior. The TDCIMS, which enables real-time measurements of composition for freshly nucleated particles as small as 8 nm and was developed with support from DOE, is the most important tool in this work. Our most important discoveries about processes that affect growth rates are summarized in a recent PNAS article (doi:10.1073/pnas.0912127107). In short, this work has shown that alkylammonium-carboxylate salts, formed, for example, by reactions between amines and carboxylic acids, account for 20–50% of the mass of freshly nucleated particles in locations that include Atlanta, Mexico City, Boulder, and Hyytiälä, while sulfates account for only about 10%. These newly discovered compounds help to explain the high growth rates of freshly nucleated particles that have been observed around the globe and help to explain why nucleation is an important atmospheric process, not just a scientific curiosity. Our poster will provide an overview of this work

Observations of aminium salts in atmospheric nanoparticles and possible climatic implications

We present laboratory studies and field observations that explore the role of aminium salt formation in atmospheric nanoparticle growth. These measurements were performed using the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) and Ultrafine Hygroscopicity Tandem Differential Mobility Analyzers. Laboratory measurements of alkylammonium—carboxylate salt nanoparticles show that these particles exhibit lower volatilities and only slightly lower hygroscopicities than ammonium sulfate nanoparticles. TDCIMS measurements of these aminium salts showed that the protonated amines underwent minimal decomposition during analysis, with detection sensitivities comparable to those of organic and inorganic deprotonated acids. TDCIMS observations made of a new particle formation event in an urban site in Tecamac, Mexico, clearly indicate the presence of protonated amines in 8–10 nm diameter particles accounting for about 47% of detected positive ions; 13 nm particles were hygroscopic with an average 90% RH growth factor of 1.42. Observations of a new particle formation event in a remote forested site in Hyytiälä, Finland, show the presence of aminium ions with deprotonated organic acids; 23% of the detected positive ions during this event are attributed to aminium salts while 10 nm particles had an average 90% RH growth factor of 1.27. Similar TDCIMS observations during events in Atlanta and in the vicinity of Boulder, Colorado, show that aminium salts accounted for 10–35% of detected positive ions. We conclude that aminium salts contribute significantly to nanoparticle growth and must be accounted for in models to accurately predict the impact of new particle formation on climate

Atmospheric measurements of the terrestrial O2 : CO2 exchange ratio of a midlatitude forest

Measurements of atmospheric O2 have been used to quantify large-scale fluxes of carbon between the oceans, atmosphere and land since 1992 (Keeling and Shertz, 1992). With time, datasets have grown and estimates of fluxes have become more precise, but a key uncertainty in these calculations is the exchange ratio of O2 and CO2 associated with the net land carbon sink (B). We present measurements of atmospheric O2 and CO2 collected over a 6-year period from a mixed deciduous forest in central Massachusetts, USA (42.537 N, 72.171 W). Using a differential fuel-cellbased instrument for O2 and a nondispersive infrared analyzer for CO2, we analyzed airstreams collected within and 5m above the forest canopy. Averaged over the entire period of record, we find these two species covary with a slope of -1:081±0:007 mol of O2 per mole of CO2 (the mean and standard error of 6 h periods). If we limit the data to values collected on summer days within the canopy, the slope is -1:03±0:01. These are the conditions in which biotic influences are most likely to dominate. This result is significantly different from the value of -1.1 widely used in O2-based calculations of the global carbon budget, suggesting the need for a deeper understanding of the exchange ratios of the various fluxes and pools comprising the net sink