Search for: All records

Abstract. Ammonia and amines play critical roles in secondary aerosol formation, especially in urban environments. However, fast measurements of ammonia and amines in the atmosphere are very scarce. We measured ammonia and amines with a chemical ionization mass spectrometer (CIMS) at the urban center in Houston, Texas, the fourth most populated urban site in the United States, during October 2022. Ammonia concentrations were on average four parts per billion by volume (ppbv), while the concentration of an individual amine ranged from several parts per trillion by volume (pptv) to hundreds of pptv. These reduced nitrogen compounds were more abundant during weekdays than on weekends and correlated with measured CO concentrations, implying they were mostly emitted from pollutant sources. Both ammonia and amines showed a distinct diurnal cycle, with higher concentrations in the warmer afternoon, indicating dominant gas-to-particle conversion processes taking place with the changing ambient temperatures. Studies have shown that dimethylamine is critical for new particle formation (NPF) in the polluted boundary layer, but currently there are no amine emission inventories in global climate models (as opposed to ammonia). Our observations made in the very polluted area of Houston, as well as a less polluted site (Kent, Ohio) from our previous study (You et al., 2014), indicate there is a consistent ratio of dimethylamine over ammonia at these two sites. Thus, our observations can provide a relatively constrained proxy of dimethylamine using 0.1 % ammonia concentrations at polluted sites in the United States to model NPF processes. 

Abstract New particle formation (NPF) has been observed at various locations, but NPF does not occur in isoprene‐dominant forests. Recent laboratory studies were conducted to understand the role of isoprene in biogenic NPF, and these studies show that isoprene can suppress biogenic NPF, with contradicting theories. To reconcile these discrepancies, we conducted flow tube experiments of biogenic nucleation under a wide range of isoprene over monoterpene carbon ratios (R) and oxidant conditions (OH vs. ozone). Our results show isoprene either suppresses or enhances biogenic NPF, depending onRand oxidation regimes, demonstrating the synergetic effects of isoprene and HO_x(OH and HO₂) on biogenic NPF. Whereas the suppression of NPF by isoprene is due to the product suppression effects of monoterpene dimers (C20), RO₂ + HO₂termination reactions also play important roles in suppressing the dimer formation, another likely process to suppress NPF in the atmosphere. 

Abstract. New particle formation (NPF) consists of two steps: nucleation andsubsequent growth. At present, chemical and physical mechanisms that governthese two processes are not well understood. Here, we report initial resultsobtained from the TANGENT (Tandem Aerosol Nucleation and Growth EnvironmentTube) experiments. The TANGENT apparatus enables us to study these twoprocesses independently. The present study focuses on the effects oftemperature on sulfuric acid nucleation and further growth. Our results showthat lower temperatures enhance both the nucleation and growth rate.However, under temperatures below 268 K the effects of temperature on thenucleation rate become less significant and the nucleation rate becomes lessdependent on relative humidity, indicating that particle formation in the conditions of ourflow tube takes place via barrierless nucleation at lower temperatures. Wealso examined the growth of newly formed particles under differingtemperature conditions for nucleation and further growth. Our results showthat newly nucleated clusters formed at low temperatures can indeed surviveevaporation and grow in a warmer environment in the presence of SO2 andozone and potentially other contaminant vapors. These results implythat some heterogeneous reactions involving nanoparticles affect nucleationand growth of newly formed particles. 

Abstract The effect of sulfur dioxide on particle formation and growth by ozonolysis of three monoterpenes (α‐pinene,β‐pinene, and limonene) and isoprene was investigated in the presence of monodisperse ammonium sulfate seed particles and an OH scavenger in a flow tube under dry conditions. Without sulfur dioxide, new particle formation was not observed, and seed particle growth was consistent with condensation of low‐volatility oxidation products produced from each organic precursor. With sulfur dioxide, new particle formation was observed from every precursor studied, consistent with sulfuric acid formation by reaction of sulfur dioxide with stabilized Criegee Intermediates. The presence of sulfur dioxide did not significantly affect seed particle growth rates fromα‐pinene and limonene ozonolysis, although chemical composition measurements revealed the presence of organosulfates in the particles following SO₂exposure. Contrarily, the growth of seeds byβ‐pinene and isoprene ozonolysis was considerably enhanced by sulfur dioxide, and chemical composition measurements revealed that the enhanced growth was not due to additional organic material, suggesting that inorganic sulfate was likely responsible. The results suggest that a previously unconsidered particle‐phase pathway to growth activated by sulfur dioxide may alter production of cloud condensation nuclei over regions with significant SO₂‐alkene interactions.