skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Chemical composition of nanoparticles from <i>α</i>-pinene nucleation and the influence of isoprene and relative humidity at low temperature
Abstract. Biogenic organic precursors play an important role inatmospheric new particle formation (NPF). One of the major precursor speciesis α-pinene, which upon oxidation can form a suite of productscovering a wide range of volatilities. Highly oxygenated organic molecules(HOMs) comprise a fraction of the oxidation products formed. While it isknown that HOMs contribute to secondary organic aerosol (SOA) formation,including NPF, they have not been well studied in newly formed particles dueto their very low mass concentrations. Here we present gas- and particle-phase chemical composition data from experimental studies of α-pinene oxidation, including in the presence of isoprene, at temperatures(−50 and −30 ∘C) and relativehumidities (20 % and 60 %) relevant in the upper free troposphere. Themeasurements took place at the CERN Cosmics Leaving Outdoor Droplets (CLOUD)chamber. The particle chemical composition was analyzed by a thermaldesorption differential mobility analyzer (TD-DMA) coupled to a nitratechemical ionization–atmospheric pressure interface–time-of-flight(CI-APi-TOF) mass spectrometer. CI-APi-TOF was used for particle- and gas-phase measurements, applying the same ionization and detection scheme. Ourmeasurements revealed the presence of C8−10 monomers and C18−20dimers as the major compounds in the particles (diameter up to∼ 100 nm). Particularly, for the system with isoprene added,C5 (C5H10O5−7) and C15 compounds(C15H24O5−10) were detected. This observation is consistentwith the previously observed formation of such compounds in the gas phase. However, although the C5 and C15 compounds do not easily nucleate,our measurements indicate that they can still contribute to the particlegrowth at free tropospheric conditions. For the experiments reported here,most likely isoprene oxidation products enhance the growth of particleslarger than 15 nm. Additionally, we report on the nucleation rates measuredat 1.7 nm (J1.7 nm) and compared with previous studies, we found lowerJ1.7 nm values, very likely due to the higher α-pinene andozone mixing ratios used in the present study.  more » « less
Award ID(s):
1801897 1801574 1801280
PAR ID:
10311362
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; more » ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; « less
Date Published:
Journal Name:
Atmospheric Chemistry and Physics
Volume:
21
Issue:
22
ISSN:
1680-7324
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. 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
  2. Reduced-nitrogen compounds (RNC), such as ammonia and amines, play important roles in atmospheric aerosol nucleation, secondary organic aerosol (SOA), and cloud formation processes. Fast measurements of ammonia and amines are made with a chemical ionization mass spectrometer (CIMS). Clusters containing RNC are measured with an atmospheric pressure interface time of flight mass spectrometer (APi-TOF) or chemical ionization APi-TOF (CI-APi-TOF). Aerosol-phase amines can be detected with a single particle mass spectrometer at real-time, or with offline chemical analytical methods using filter samples. However, the application of these instruments in real atmospheric measurements is still very limited. This perspective article highlights recent measurements of RNC in the atmosphere and discusses their implications in new particle formation (NPF). 
    more » « less
  3. Abstract. Secondary organic aerosols (SOA) are major components of atmospheric fineparticulate matter, affecting climate and air quality. Mounting evidenceexists that SOA can adopt glassy and viscous semisolid states, impactingformation and partitioning of SOA. In this study, we apply the GECKO-A(Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere)model to conduct explicit chemical modeling of isoprene photooxidation andα-pinene ozonolysis and their subsequent SOA formation. The detailedgas-phase chemical schemes from GECKO-A are implemented into a box model andcoupled to our recently developed glass transition temperatureparameterizations, allowing us to predict SOA viscosity. The effects ofchemical composition, relative humidity, mass loadings and mass accommodation on particle viscosity are investigated in comparison withmeasurements of SOA viscosity. The simulated viscosity of isoprene SOAagrees well with viscosity measurements as a function of relative humidity,while the model underestimates viscosity of α-pinene SOA by a feworders of magnitude. This difference may be due to missing processes in themodel, including autoxidation and particle-phase reactions, leading to theformation of high-molar-mass compounds that would increase particleviscosity. Additional simulations imply that kinetic limitations of bulkdiffusion and reduction in mass accommodation coefficient may play a role inenhancing particle viscosity by suppressing condensation of semi-volatilecompounds. The developed model is a useful tool for analysis andinvestigation of the interplay among gas-phase reactions, particle chemicalcomposition and SOA phase state. 
    more » « less
  4. Biogenic vapors form new particles in the atmosphere, affecting global climate. The contributions of monoterpenes and isoprene to new particle formation (NPF) have been extensively studied. However, sesquiterpenes have received little attention despite a potentially important role due to their high molecular weight. Via chamber experiments performed under atmospheric conditions, we report biogenic NPF resulting from the oxidation of pure mixtures of β-caryophyllene, α-pinene, and isoprene, which produces oxygenated compounds over a wide range of volatilities. We find that a class of vapors termed ultralow-volatility organic compounds (ULVOCs) are highly efficient nucleators and quantitatively determine NPF efficiency. When compared with a mixture of isoprene and monoterpene alone, adding only 2% sesquiterpene increases the ULVOC yield and doubles the formation rate. Thus, sesquiterpene emissions need to be included in assessments of global aerosol concentrations in pristine climates where biogenic NPF is expected to be a major source of cloud condensation nuclei. 
    more » « less
  5. Abstract. Oxygenated organic molecules (OOMs) play an important role in the formation of atmospheric aerosols. Due to various analytical challenges with respect to measuring organic vapors, uncertainties remain regarding the formation and fate of OOMs. The chemical ionization Orbitrap (CI-Orbitrap) mass spectrometer has recently been shown to be a powerful technique that is able to accurately identify gaseous organic compounds due to its greater mass resolution. Here, we present the ammonium-ion-based CI-Orbitrap (NH4+-Orbitrap) as a technique capable of measuring a wide range of gaseous OOMs. The performance of the NH4+-Orbitrap is compared with that of state-of-the-art mass spectrometers, including a nitrate-ion-based chemical ionization atmospheric pressure interface coupled to a time-of-flight mass spectrometer (NO3--LTOF), a new generation of proton transfer reaction-TOF mass spectrometer (PTR3-TOF), and an iodide-based CI-TOF mass spectrometer equipped with a Filter Inlet for Gases and AEROsols (I−-CIMS). The instruments were deployed simultaneously in the Cosmic Leaving OUtdoors Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN) during the CLOUD14 campaign in 2019. Products generated from α-pinene ozonolysis under various experimental conditions were simultaneously measured by the mass spectrometers. The NH4+-Orbitrap was able to identify the widest range of OOMs (i.e., O ≥ 2), from less-oxidized species to highly oxygenated organic molecules (HOMs). Excellent agreement was found between the NH4+-Orbitrap and the NO3--LTOF with respect to characterizing HOMs and with the PTR3-TOF for the less-oxidized monomeric species. OOM concentrations measured by NH4+-Orbitrap were estimated using calibration factors derived from the OOMs with high time-series correlations during the side-by-side measurements. As with the other mass spectrometry techniques used during this campaign, the detection sensitivity of the NH4+-Orbitrap to OOMs is greatly affected by relative humidity, which may be related to changes in ionization efficiency and/or multiphase chemistry. Overall, this study shows that NH4+-ion-based chemistry associated with the high mass resolution of the Orbitrap mass analyzer can measure almost all inclusive compounds. As a result, it is now possible to cover the entire range of compounds, which can lead to a better understanding of the oxidation processes. 
    more » « less