Hydroxyl radical (·OH)-initiated oxidation of isoprene, the most abundant nonmethane hydrocarbon in the atmosphere, is responsible for substantial amounts of secondary organic aerosol (SOA) within ambient fine particles. Fine particulate 2-methyltetrol sulfate diastereoisomers (2-MTSs) are abundant SOA products formed via acid-catalyzed multiphase chemistry of isoprene-derived epoxydiols with inorganic sulfate aerosols under low-nitric oxide conditions. We recently demonstrated that heterogeneous ·OH oxidation of particulate 2-MTSs leads to the particle-phase formation of multifunctional organosulfates (OSs). However, it remains uncertain if atmospheric chemical aging of particulate 2-MTSs induces toxic effects within human lung cells. We show that inhibitory concentration-50 (IC50) values decreased from exposure to
fine particulate 2-MTSs that were heterogeneously aged for 0 to 22 days by ·OH, indicating increased particulate toxicity in BEAS-2B lung cells. Lung cells further exhibited concentration-dependent modulation of oxidative stress- and inflammatory-related gene expression. Principal component analysis was carried out on the chemical mixtures and revealed positive correlations between exposure to aged multifunctional OSs and altered expression of targeted genes. Exposure to particulate 2-MTSs alone was associated with an altered expression of antireactive oxygen species (ROS)-related genes (NQO-1, SOD-2, and CAT) indicative of a response to ROS in the cells. Increased aging of particulate 2-MTSs by ·OH exposure was associated with an increased expression of glutathione pathway related genes (GCLM and GCLC) and an anti-inflammatory gene (IL-10).
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Organosulfates Are Primarily Deprotonated at Atmospheric Aerosol Acidities: pH‐Dependent Protonation State via Raman and Infrared Spectroscopy.
Secondary organic aerosol (SOA) is a significant
component of atmospheric fine particulate matter
(PM2.5) globally that can form through multiphase
chemistry of oxidized volatile organic compounds (VOC)
leading to lower‐volatility particulate species. Condensed
phase reactions of certain SOA constituents with
inorganic sulfate derived from SO2 oxidation will lead to
the formation of organosulfates, which can account for
up to 10 – 15% of the organic mass within PM2.5. Despite
the ubiquitous presence of atmospheric fine particulate
organosulfates, our fundamental understanding of the
molecular structure of organosulfates is limited,
including for 2‐methyltetrol organosulfates (2‐MTSs),
which are typically the single most abundant
organosulfates measured in PM2.5, formed from isoprene
oxidation products. As atmospheric aerosol pH varies
widely (0 – 6), it is important to know whether
organosulfates exist primarily in their protonated
(ROSO3H) or deprotonated (ROSO3
‐) forms. In this study,
vibrational modes of synthetically‐pure 2‐MTSs were
spectroscopically probed using Raman and infrared (IR)
spectroscopies, supported by density functional theory
(DFT) of the protonated and deprotonated structures.
Vibrational bands at 1035 and 1059 cm‐1 were seen in
both the IR and Raman spectra, and were associated
with the ROSO3
‐ anion by comparison to DFT
calculations. Analysis of Raman spectra across a range of
acidities (pH = 0 – 10) shows that 2‐MTSs are
deprotonated (ROSO3
‐) at those pH values. Additional
DFT calculations for organosulfates derived from
isoprene, α‐pinene, β‐caryophyllene, and toluene
suggest that most organosulfates exist in their
deprotonated form (ROSO3
‐) in atmospheric particles.
These charged species may have significant implications
for our understanding of aerosol acidity and should be
considered in thermodynamic model calculations.
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- Award ID(s):
- 2001027
- NSF-PAR ID:
- 10313545
- Date Published:
- Journal Name:
- 2021 AAAR 39th Annual Conference
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Kinetics and Products of Heterogeneous Hydroxyl Radical Oxidation of Isoprene Epoxydiol‐Derived SOA.In isoprene‐rich regions, acid‐catalyzed multiphase reactions of isoprene epoxydiols (IEPOX) with inorganic sulfate (Sulfinorg) particles form secondary organic aerosol (IEPOX‐SOA), extensively converting Sulfinorg to lowervolatility particulate organosulfates (OSs), including 2‐ methyltetrol sulfates (2‐MTSs) and their dimers. Recently, we showed that heterogeneous hydroxyl radical (OH) oxidation of particulate 2‐MTSs generated multifunctional OS products. However, atmospheric models assume that OS‐rich IEPOX‐SOA particles remain unreactive towards heterogeneous OH oxidation, and limited laboratory studies have been conducted to examine the heterogeneous OH oxidation kinetics of full IEPOX‐SOA mixtures. Hence, this study investigated the kinetics and products resulting from heterogeneous OH oxidation of freshly‐generated IEPOXSOA in order to help derive model‐ready parameterizations. First, gas‐phase IEPOX was reacted with acidic Sulfinorg particles under dark conditions in order to form fresh IEPOX‐SOA particles. These particles were then subsequently aged at RH of 56% in an oxidation flow reactor at OH exposures ranging from 0~15 days of equivalent atmospheric exposure. Aged IEPOX‐SOA particles were sampled by an online aerosol chemical speciation monitor (ACSM) and collected onto Teflon filters for off‐line molecular‐level chemical analyses by hydrophilic liquid interaction chromatography method interfaced to electrospray ionization high‐resolution quadrupole time‐offlight mass spectrometry (HILIC/ESI‐HR‐QTOFMS). Our results show that heterogeneous OH oxidation only caused a 7% decay of IEPOX‐SOA by 10 days exposure, likely owing to the inhibition of reactive uptake of OH as fresh IEPOXSOA particles have an inorganic core‐organic shell morphology. A significantly higher fraction of IEPOX‐SOA (~37%) decayed by 15 days exposure, likely due to the increasing reactive uptake of OH as IEPOX‐SOA become more liquid‐like with aging. Freshly‐generated IEPOX‐SOA constituents exhibited varying degrees of aging with 2‐MTSdimers being the most reactive, followed by 2‐MTSs and 2‐ methyltetrols (2‐MTs), respectively. Notably, extensive amounts of previously characterized particle‐phase products in ambient fine aerosols were detected in our laboratory‐aged IEPOX‐SOA samples.more » « less
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Methyltetrol sulfates are unique tracers for secondary organic aerosols (SOA) formed from acid-driven multiphase chemistry of isoprene-derived epoxydiols. 2-Methyltetrol sulfate diastereomers (2-MTSs) are the dominant isomers and single most-abundant SOA tracers in atmospheric fine particulate matter (PM2.5), but their atmospheric sinks remain unknown. We investigated the oxidative aging of authentic 2-MTS aerosols by gas-phase hydroxyl radicals (•OH) at a relative humidity of 61 ± 1%. The effective rate constant for this heterogeneous reaction was determined as 4.9 ± 0.6 × 10–13 cm3 molecules–1 s–1, corresponding to an atmospheric lifetime of 16 ± 2 days (assuming an •OH concentration of 1.5 × 106 molecules cm–3). Chemical changes to 2-MTSs were monitored by hydrophilic interaction liquid chromatography interfaced to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (HILIC/ESI-HR-QTOFMS). Plausible reaction mechanisms are proposed for previously unknown OSs detected in atmospheric PM2.5 at mass-to-charge ratios (m/z) of 139 (C2H3O5S–), 155 (C2H3O6S–), 169 (C3H5O6S–), 171 (C3H7O6S–), 185 (C3H5O7S–), 199 (C4H7O7S–), 211 (C5H7O7S–), 213 (C5H9O7S–), 227 (C5H7O8S–), 229 (C5H9O8S–), and 231 (C5H11O8S–). Heterogeneous •OH oxidation of 2-MTSs redistributes the particulate sulfur speciation into more oxygenated/functionalized OSs, likely modifying the aerosol physicochemical properties of SOA containing 2-MTSs.more » « less
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