skip to main content


Title: Effects of particle phase acidity and gaseous ammonia on the heterogenous interactions between amines and ambient aerosol
Recent research in atmospheric chemistry suggested that gaseous amines may rapidly react with the acidic components in the aerosol to be incorporated in the particle phase. However, laboratory experiments suggested that these heterogeneous processes may be sensitive to the reaction conditions, such as relative humidity (RH), the initial aerosol acidity and the initial concentration of gaseous ammonia which is ubiquitous in the atmosphere. We studied the heterogenous reactions between several amines and ammonium sulfate using a series of thermodynamic simulations under varying initial conditions, including RH, particle-phase acidity and gaseous amine and ammonia concentrations. Several distinctively different trends in the particle-phase ammonium, amines and water content were observed, depending significantly on the particle-phase acidity and the initial amine to ammonia mole ratio. One notable observation was that alkylamines may facilitate the water uptake of ammonium sulfate even in the presence of 1000 times more ammonia gas. Such change in aerosol water content may alter the surface tension, uptake coefficient and could formation properties of aerosol and influence the radiative forcing of the particles.  more » « less
Award ID(s):
1847019
NSF-PAR ID:
10330198
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
The 262nd American Chemical Society National Meeting & Exposition
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Sea salt aerosols contribute significantly to the mass loading of ambient aerosol, which may serve as cloud condensation nuclei and can contribute to light scattering in the atmosphere. Two major chemical components commonly found in sea salts are ammonium sulfate (AS) and sodium chloride (NaCl). It has been shown that alkylamines, derivatives of ammonia, can react with ammonium salts in the particle-phase to displace ammonia and likely change the particle properties. This study investigated the effects of atmospheric alkylamines on the composition and properties of sea salt aerosols using a chemical system of methylamine (MA, as a proxy of alkylamines), AS and NaCl (as a proxy of sea salt aerosol). The concentrations of ammonia and MA in aqueous/gas phases at the thermodynamic equilibrium were determined using the Extended Aerosols and Inorganics Model (E-AIM) under varying initial inputs, along with the deliquescence relative humidity (DRH) and the corresponding particle water content. Our findings indicated a notable negative relationship between MA concentration and the DRH for both AS and NaCl while the effect of MA on NaCl is smaller than that on AS. The salt of MA in the particle phase may absorb water vapor and may lead to the displacement reaction between AS and NaCl due to the low solubility of sodium sulfate. The acidity in the particle phase also played a significant role in affecting the DRH of sea salt aerosols. Since both sea salt aerosol and alkylamines are emitted into the atmosphere from the ocean in large quantities, our study suggested the potential impact of alkylamines on the environment and the climate via the modification of sea salt aerosol properties. 
    more » « less
  2. Isoprene has a strong effect on the oxidative capacity of the troposphere due to its abundance. Under low-NOx conditions, isoprene oxidizes to form isoprene-derived epoxydiols (IEPOX), contributing significantly to secondary organic aerosol (SOA) through heterogeneous reactions. In particular, organosulfates (OSs) can form from acid-driven reactive uptake of IEPOX onto preexisting particles followed by nucleophilic addition of inorganic sulfate, and they are an important component of SOA mass, primarily in submicron particles with long atmospheric lifetimes. Fundamental understanding of SOA and OS evolution in particles, including the formation of new compounds by oxidation as well as corresponding viscosity changes, is limited, particularly across relative humidity (RH) conditions above and below the deliquescence of typical sulfate aerosol particles. In a 2-m3 indoor chamber held at various RH values (30 – 80%), SOA was generated from reactive uptake of gas-phase IEPOX onto acidic ammonium sulfate aerosols (pH = 0.5 – 2.5) and then aged in an oxidation flow reactor (OFR) for 0 – 24 days of equivalent atmospheric ·OH exposure. We investigated the extent of inorganic sulfate conversion to organosulfate, formation of oligomers, single-particle physicochemical properties, such as viscosity and phase state, and oxidation kinetics. Chemical composition of particle-phase species, as well as aerosol morphological changes, are analyzed as a function of RH, oxidant exposure times, and particle acidity to better understand SOA and OS formation and destruction mechanisms in the ambient atmosphere. 
    more » « less
  3. The reactive partitioning of cis and trans β-IEPOX was investigated on hydrated inorganic seed particles, without the addition of acids. No organic aerosol (OA) formation was observed on dry ammonium sulfate (AS); however, prompt and efficient OA growth was observed for the cis and trans β-IEPOX on AS seeds at liquid water contents of 40–75% of the total particle mass. OA formation from IEPOX is a kinetically limited process, thus the OA growth continues if there is a reservoir of gas-phase IEPOX. There appears to be no differences, within error, in the OA growth or composition attributable to the cis / trans isomeric structures. Reactive uptake of IEPOX onto hydrated AS seeds with added base (NaOH) also produced high OA loadings, suggesting the pH dependence for OA formation from IEPOX is weak for AS particles. No OA formation, after particle drying, was observed on seed particles where Na+ was substituted for NH4+. The Henry's Law partitioning of IEPOX was measured on NaCl particles (ionic strength ~9 M) to be 3 × 107 M atm−1 (−50 / +100%). A small quantity of OA was produced when NH4+ was present in the particles, but the chloride (Cl-) anion was substituted for sulfate (SO42-), possibly suggesting differences in nucleophilic strength of the anions. Online time-of-flight aerosol mass spectrometry and offline filter analysis provide evidence of oxygenated hydrocarbons, organosulfates, and amines in the particle organic composition. The results are consistent with weak correlations between IEPOX-derived OA and particle acidity or liquid water observed in field studies, as the chemical system is nucleophile-limited and not limited in water or catalyst activity.

     
    more » « less
  4. Abstract

    Transformation of low-volatility gaseous precursors to new particles affects aerosol number concentration, cloud formation and hence the climate. The clustering of acid and base molecules is a major mechanism driving fast nucleation and initial growth of new particles in the atmosphere. However, the acid–base cluster composition, measured using state-of-the-art mass spectrometers, cannot explain the measured high formation rate of new particles. Here we present strong evidence for the existence of base molecules such as amines in the smallest atmospheric sulfuric acid clusters prior to their detection by mass spectrometers. We demonstrate that forming (H2SO4)1(amine)1 is the rate-limiting step in atmospheric H2SO4-amine nucleation and the uptake of (H2SO4)1(amine)1 is a major pathway for the initial growth of H2SO4 clusters. The proposed mechanism is very consistent with measured new particle formation in urban Beijing, in which dimethylamine is the key base for H2SO4 nucleation while other bases such as ammonia may contribute to the growth of larger clusters. Our findings further underline the fact that strong amines, even at low concentrations and when undetected in the smallest clusters, can be crucial to particle formation in the planetary boundary layer.

     
    more » « less
  5. In order to examine the reaction products, kinetics, and implications of ISOPOOH with aqueous sulfite, ammonium bisulfate particles were injected into the UNC 10‐m3 indoor environmental chamber under humid (i.e., 72% RH) and dark conditions. After the inorganic sulfate concentration stabilized, selected concentrations of gas‐phase 1,2‐ISOPOOH were injected into the chamber, and aerosols showed a minimal mass increase. Gaseous SO2 was subsequently injected into the chamber and a significant amount of aerosol mass was produced. The gas‐phase ISOPOOH and particle‐phase species were sampled with online instruments, including a chemical ionization mass spectrometer (CIMS), an aerosol chemical speciation monitor (ACSM), a particle‐into‐liquid sampler (PILS) for analysis by ion chromatography analysis (IC), and filter samples were analyzed by an ultra‐performance liquid chromatography coupled to an electrospray ionization highresolution quadrupole time‐of‐flight mass spectrometry (UPLCESI‐ HR‐QTOFMS) to obtain offline molecular‐level information. Results show that a significant amount of inorganic sulfate and organosulfates were formed rapidly after injecting SO2, altering the chemical and physical properties of the particles including phase state, pH, reactivity, and composition. Multifunctional C5‐organic species that were previously measured in atmospheric fine aerosol samples were also reported here as reaction products, including 2‐methyletrols and 2‐methyltetrol sulfates that were previously thought to be only produced from the reactive uptake of isoprene‐derived epoxydiols (IEPOX). Such results indicate that the multiphase reactions of ISOPOOH could have significant impacts on the atmospheric lifecycle of organic aerosols and sulfur, as well as the physicochemical properties of ambient particles. 
    more » « less