More Like this

1. Relative humidity effect on the formation of highly oxidized molecules and new particles during monoterpene oxidation

   https://doi.org/10.5194/acp-19-1555-2019  

   Li, Xiaoxiao; Chee, Sabrina; Hao, Jiming; Abbatt, Jonathan P.; Jiang, Jingkun; Smith, James N. (January 2019, Atmospheric Chemistry and Physics)

   Abstract. It has been widely observed around the world that the frequency and intensityof new particle formation (NPF) events are reduced during periods of highrelative humidity (RH). The current study focuses on how RH affects theformation of highly oxidized molecules (HOMs), which are key components ofNPF and initial growth caused by oxidized organics. The ozonolysis ofα-pinene, limonene, and Δ³-carene, with and without OHscavengers, were carried out under low NO_x conditions undera range of RH (from ∼3 % to ∼92 %) in atemperature-controlled flow tube to generate secondary organic aerosol (SOA).A Scanning Mobility Particle Sizer (SMPS) was used to measure the sizedistribution of generated particles, and a novel transverse ionizationchemical ionization inlet with a high-resolution time-of-fight massspectrometer detected HOMs. A major finding from this work is that neitherthe detected HOMs nor their abundance changed significantly with RH, whichindicates that the detected HOMs must be formed from water-independentpathways. In fact, the distinguished OH- and O₃-derived peroxyradicals (RO₂), HOM monomers, and HOM dimers could mostly beexplained by the autoxidation of RO₂ followed by bimolecularreactions with other RO₂ or hydroperoxy radicals (HO₂),rather than from a water-influenced pathway like through the formation of astabilized Criegee intermediate (sCI). However, as RH increased from ∼3 % to ∼92 %, the total SOA number concentrations decreased bya factor of 2–3 while SOA mass concentrations remained relatively constant. These observations show that, whilehigh RH appears to inhibit NPF as evident by the decreasing numberconcentration, this reduction is not caused by a decrease inRO₂-derived HOM formation. Possible explanations for these phenomenawere discussed. 

   more » « less
2. Observations of biogenic volatile organic compounds over a mixed temperate forest during the summer to autumn transition

   https://doi.org/10.5194/acp-23-4123-2023  

   Vermeuel, Michael P.; Novak, Gordon A.; Kilgour, Delaney B.; Claflin, Megan S.; Lerner, Brian M.; Trowbridge, Amy M.; Thom, Jonathan; Cleary, Patricia A.; Desai, Ankur R.; Bertram, Timothy H. (January 2023, Atmospheric Chemistry and Physics)

   Abstract. The exchange of trace gases between the biosphere and the atmosphere is an important process that controls both chemical and physical properties of the atmosphere with implications for air quality and climate change. The terrestrial biosphere is a major source of reactive biogenic volatile organic compounds (BVOCs) that govern atmospheric concentrations of the hydroxy radical (OH) and ozone (O3) and control the formation andgrowth of secondary organic aerosol (SOA). Common simulations of BVOCsurface–atmosphere exchange in chemical transport models use parameterizations derived from the growing season and do not considerpotential changes in emissions during seasonal transitions. Here, we useobservations of BVOCs over a mixed temperate forest in northern Wisconsinduring broadleaf senescence to better understand the effects of the seasonal changes in canopy conditions (e.g., temperature, sunlight, leaf area, and leaf stage) on net BVOC exchange. The BVOCs investigated here include the terpenoids isoprene (C5H8), monoterpenes (MTs; C10H16), a monoterpene oxide (C10H16O), and sesquiterpenes (SQTs; C15H24), as well as a subset of other monoterpene oxides and dimethyl sulfide (DMS). During this period, MTs were primarily composed of α-pinene, β-pinene, and camphene, with α-pinene and camphene dominant during the first half of September and β-pinene thereafter. We observed enhanced MT and monoterpene oxide emissions following the onset of leaf senescence and suggest that senescence has the potential to be a significant control on late-season MT emissions in this ecosystem. We show that common parameterizations of BVOC emissions cannot reproduce the fluxes of MT, C10H16O, and SQT during the onset and continuation of senescence but can correctly simulate isoprene flux. We also describe the impact of the MT emission enhancement on the potential to form highly oxygenated organic molecules (HOMs). The calculated production rates of HOMs and H2SO4, constrained by terpene and DMS concentrations, suggest that biogenic aerosol formation and growth in this region should be dominated by secondary organics rather than sulfate. Further, we show that models using parameterized MT emissions likely underestimate HOM production, and thus aerosol growth and formation, during early autumn in this region. Further measurements of forest–atmosphere BVOC exchange during seasonal transitions as well as measurements of DMS in temperate regions are needed to effectively predict the effects of canopy changes on reactive carbon cycling and aerosol production. 

   more » « less
3. Effects of topography on in‐canopy transport of gases emitted within dense forests

   https://doi.org/10.1002/qj.3546  

   Chen, Bicheng; Chamecki, Marcelo; Katul, Gabriel G. (May 2019, Quarterly Journal of the Royal Meteorological Society)

   The significance of air flow within dense canopies situated on hilly terrain is not in dispute given its relevance to a plethora of applications in meteorology, wind energy, air pollution, atmospheric chemistry and ecology. While the mathematical description of such flows is complex, progress has proceeded through an interplay between experiments, mathematical modelling, and more recently large‐eddy simulations (LESs). In this contribution, LES is used to investigate the topography‐induced changes in the flow field and how these changes propagate to scalar transport within the canopy. The LES runs are conducted for a neutral atmospheric boundary layer above a tall dense forested canopy situated on a train of two‐dimensional sinusoidal hills. The foliage distribution is specified using leaf area density measurements collected in an Amazon rain forest. A series of LES runs with increasing hill amplitude are conducted to disturb the flow from its flat‐terrain state. The LES runs successfully reproduce the recirculation region and the flow separation on the lee‐side of the hill within the canopy region in agreement with prior laboratory and LES studies. Simulation results show that air parcels released inside the canopy have two preferential pathways to escape the canopy region: a “local” pathway similar to that encountered in flat terrain and an “advective” pathway near the flow‐separation region. Further analysis shows that the preferential escape location over the flow‐separation region leads to a “chimney”‐like effect that becomes amplified for air parcel releases near the forest floor. The work here demonstrates that shear‐layer turbulence is the main mechanism exporting air parcels out the canopy for both pathways. However, compared to flat terrain, the mean updraught at the flow separation induced by topography significantly shortens the in‐canopy residence time for air parcels released in the lower canopy, thus enhancing the export fraction of reactive gases. 

   more » « less
4. Size-dependent influence of NO _x on the growth rates of organic aerosol particles

   https://doi.org/10.1126/sciadv.aay4945  

   Yan, C.; Nie, W.; Vogel, A. L.; Dada, L.; Lehtipalo, K.; Stolzenburg, D.; Wagner, R.; Rissanen, M. P.; Xiao, M.; Ahonen, L.; et al (May 2020, Science Advances)

   null (Ed.)

   Atmospheric new-particle formation (NPF) affects climate by contributing to a large fraction of the cloud condensation nuclei (CCN). Highly oxygenated organic molecules (HOMs) drive the early particle growth and therefore substantially influence the survival of newly formed particles to CCN. Nitrogen oxide (NO x ) is known to suppress the NPF driven by HOMs, but the underlying mechanism remains largely unclear. Here, we examine the response of particle growth to the changes of HOM formation caused by NO x . We show that NO x suppresses particle growth in general, but the suppression is rather nonuniform and size dependent, which can be quantitatively explained by the shifted HOM volatility after adding NO x . By illustrating how NO x affects the early growth of new particles, a critical step of CCN formation, our results help provide a refined assessment of the potential climatic effects caused by the diverse changes of NO x level in forest regions around the globe. 

   more » « less
5. Molecular understanding of new-particle formation from <i>α</i>-pinene between −50 and +25 °C

   https://doi.org/10.5194/acp-20-9183-2020  

   Simon, Mario; Dada, Lubna; Heinritzi, Martin; Scholz, Wiebke; Stolzenburg, Dominik; Fischer, Lukas; Wagner, Andrea C.; Kürten, Andreas; Rörup, Birte; He, Xu-Cheng; et al (January 2020, Atmospheric Chemistry and Physics)

   null (Ed.)

   Abstract. Highly oxygenated organic molecules (HOMs) contributesubstantially to the formation and growth of atmospheric aerosol particles,which affect air quality, human health and Earth's climate. HOMs are formedby rapid, gas-phase autoxidation of volatile organic compounds (VOCs) suchas α-pinene, the most abundant monoterpene in the atmosphere. Due totheir abundance and low volatility, HOMs can play an important role innew-particle formation (NPF) and the early growth of atmospheric aerosols,even without any further assistance of other low-volatility compounds suchas sulfuric acid. Both the autoxidation reaction forming HOMs and theirNPF rates are expected to be strongly dependent ontemperature. However, experimental data on both effects are limited.Dedicated experiments were performed at the CLOUD (Cosmics Leaving OUtdoorDroplets) chamber at CERN to address this question. In this study, we showthat a decrease in temperature (from +25 to −50 ∘C) results ina reduced HOM yield and reduced oxidation state of the products, whereas theNPF rates (J1.7 nm) increase substantially.Measurements with two different chemical ionization mass spectrometers(using nitrate and protonated water as reagent ion, respectively) providethe molecular composition of the gaseous oxidation products, and atwo-dimensional volatility basis set (2D VBS) model provides their volatilitydistribution. The HOM yield decreases with temperature from 6.2 % at 25 ∘C to 0.7 % at −50 ∘C. However, there is a strongreduction of the saturation vapor pressure of each oxidation state as thetemperature is reduced. Overall, the reduction in volatility withtemperature leads to an increase in the nucleation rates by up to 3orders of magnitude at −50 ∘C compared with 25 ∘C. Inaddition, the enhancement of the nucleation rates by ions decreases withdecreasing temperature, since the neutral molecular clusters have increasedstability against evaporation. The resulting data quantify how the interplaybetween the temperature-dependent oxidation pathways and the associatedvapor pressures affect biogenic NPF at the molecularlevel. Our measurements, therefore, improve our understanding of purebiogenic NPF for a wide range of tropospherictemperatures and precursor concentrations. 

   more » « less