Atmospheric aerosols significantly offset positive radiative forcing due to their contributions as cloud condensation nuclei (CCN) and ice nucleating particles (INPs). The cloud-aerosol-precipitation interactions in the atmosphere are determined by physical and chemical properties of aerosol particles, which can undergo many cycles of droplet activation and subsequent drying before dry or wet deposition from the atmosphere. Secondary organic aerosol (SOA) is an abundant class of aerosol and has been previously shown to contribute to aerosol formed from cloud processing. Isoprene-derived secondary organic aerosol SOA (iSOA) is a particularly important class of aerosol involved in cloud processing. iSOA has both soluble and insoluble components, but there has been a measurement gap in characterizing the insoluble components, as most analyses have focused on soluble components. These measurements are needed as previous research has suggested that insoluble components could be important with respect to CCN and INP formation. Herein, we analyze the insoluble components of SOA generated from the reactive uptake of IEPOX onto acidic seed particles (ammonium sulfate + sulfuric acid at different ratios for different pH conditions) in an atmospheric chamber. We characterize the size distributions and chemical composition, using NanoParticle Tracking Analysis (NTA), Raman microspectroscopy and atomic force microscopy infrared (AFM-IR) spectroscopy as a function of sulfate aerosol seed pH. These insights may help understand aerosol properties after cloud cycling in the atmosphere.
more »
« less
A biogenic secondary organic aerosol source of cirrus ice nucleating particles
Abstract Atmospheric ice nucleating particles (INPs) influence global climate by altering cloud formation, lifetime, and precipitation efficiency. The role of secondary organic aerosol (SOA) material as a source of INPs in the ambient atmosphere has not been well defined. Here, we demonstrate the potential for biogenic SOA to activate as depositional INPs in the upper troposphere by combining field measurements with laboratory experiments. Ambient INPs were measured in a remote mountaintop location at –46 °C and an ice supersaturation of 30% with concentrations ranging from 0.1 to 70 L –1 . Concentrations of depositional INPs were positively correlated with the mass fractions and loadings of isoprene-derived secondary organic aerosols. Compositional analysis of ice residuals showed that ambient particles with isoprene-derived SOA material can act as depositional ice nuclei. Laboratory experiments further demonstrated the ability of isoprene-derived SOA to nucleate ice under a range of atmospheric conditions. We further show that ambient concentrations of isoprene-derived SOA can be competitive with other INP sources. This demonstrates that isoprene and potentially other biogenically-derived SOA materials could influence cirrus formation and properties.
more »
« less
- NSF-PAR ID:
- 10212472
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 11
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract. This study presents a characterization of the hygroscopic growth behaviour and effects of different inorganic seed particles on the formation of secondary organic aerosols (SOAs) from the dark ozone-initiated oxidation of isoprene at low NOx conditions. We performed simulations of isoprene oxidation using a gas-phase chemical reaction mechanism based onthe Master Chemical Mechanism (MCM) in combination with an equilibriumgas–particle partitioning model to predict the SOA concentration. Theequilibrium model accounts for non-ideal mixing in liquid phases, includingliquid–liquid phase separation (LLPS), and is based on the AIOMFAC (Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients) model for mixture non-ideality and the EVAPORATION (Estimation of VApour Pressure of ORganics, Accounting for Temperature,Intramolecular, and Non-additivity effects) model for pure compound vapourpressures. Measurements from the Cosmics Leaving Outdoor Droplets (CLOUD)chamber experiments, conducted at the European Organization for NuclearResearch (CERN) for isoprene ozonolysis cases, were used to aid inparameterizing the SOA yields at different atmospherically relevanttemperatures, relative humidity (RH), and reacted isoprene concentrations. To represent the isoprene-ozonolysis-derived SOA, a selection of organicsurrogate species is introduced in the coupled modelling system. The modelpredicts a single, homogeneously mixed particle phase at all relativehumidity levels for SOA formation in the absence of any inorganic seedparticles. In the presence of aqueous sulfuric acid or ammonium bisulfateseed particles, the model predicts LLPS to occur below ∼ 80 % RH, where the particles consist of an inorganic-rich liquid phase andan organic-rich liquid phase; however, this includes significant amounts of bisulfate and water partitioned to the organic-rich phase. The measurements show an enhancement in the SOA amounts at 85 % RH, compared to 35 % RH, for both the seed-free and seeded cases. The model predictions of RH-dependent SOA yield enhancements at 85 % RH vs. 35 % RH are 1.80 for a seed-free case, 1.52 for the case with ammonium bisulfate seed, and 1.06 for the case with sulfuric acid seed. Predicted SOA yields are enhanced in the presence of an aqueous inorganic seed, regardless of the seed type (ammonium sulfate, ammonium bisulfate, or sulfuric acid) in comparison with seed-free conditions at the same RH level. We discuss the comparison of model-predicted SOA yields with a selection of other laboratory studies on isoprene SOA formation conducted at different temperatures and for a variety of reacted isoprene concentrations. Those studies were conducted at RH levels at or below 40 % with reported SOA mass yields ranging from 0.3 % up to 9.0 %, indicating considerable variations. A robust feature of our associated gas–particle partitioning calculations covering the whole RH range is the predicted enhancement of SOA yield at high RH (> 80 %) compared to low RH (dry) conditions, which is explained by the effect of particle water uptake and its impact on the equilibrium partitioning of all components.more » « less
-
Atmospheric aerosols are key contributors to cloud condensation nuclei (CCN) and ice nucleating particle (INP) formation, which can offset positive radiative forcing. Aerosol particles can undergo many cycles of droplet activation and subsequent drying before their removal from the atmosphere through dry or wet deposition. Cloud-aerosol-precipitation interactions are affected by cloud droplet or ice crystal formation, which is related to the physicochemical properties of aerosol particles. Isoprene-derived secondary organic aerosol (iSOA) is an abundant component aerosol and has been previously found in INPs and cloud water residues, and it includes both soluble and insoluble residues in its particle matrix. Currently, most of our understanding of iSOA is derived from studying the soluble residues, but there has been a measurement gap for characterizing the insoluble residues. These measurements are needed as previous research has suggested that insoluble components could be important with respect to CCN and INP formation. Herein, a unique approach is utilized to collect the insoluble residues of SOA in ~3 μm droplets collected from a Spot Sampler from Aerosol Devices, Inc. iSOA is generated by reactive uptake of IEPOX onto acidic seed particles (ammonium sulfate + sulfuric acid) in a humidified atmospheric chamber under dark conditions. Droplets are impacted directly on a substrate or in a liquid medium to study the roles of insoluble residues from both single-particle and bulk perspectives. A suite of microspectroscopy techniques, including Raman and optical photothermal infrared (O-PTIR) spectroscopy, are used to probe the chemical composition of the residues. Atomic force microscopy – photothermal infrared (AFM-PTIR) spectroscopy and Nanoparticle Tracking Analysis (NTA) are used to measure the size distributions of the residues. These insights may help understand the properties of residues from cloud droplet evaporation and subsequent cloud-aerosol-precipitation interactions in the atmosphere.more » « less
-
Isoprene is one of the most common biogenic volatile organic compounds (BVOC) in the atmosphere, produced by many plants. Isoprene undergoes oxidation to form gaseous isoprene epoxydiols (IEPOX) under low-NOx conditions, which can lead to the formation of secondary organic aerosol (SOA) particles. SOA-containing particles affect climate by scattering and absorbing solar radiation or acting as cloud condensation nuclei (CCN). High concentrations of SOA are also associated with adverse health impacts in people. While in the atmosphere, IEPOX SOA particles continue to undergo reactions with atmospheric oxidants, including hydroxyl radical (OH). To isolate and probe this process, we studied atmospheric chemical processes in an aerosol chamber to better understand the evolution of heterogeneous OH oxidation of IEPOX-derived SOA particles. Since very little is understood about the structural and spectroscopic properties because of the complexity of their many sources and atmospheric processing, individual particle measurements are necessary to provide better understanding of the composition of IEPOX SOA. We injected particles composed of mixtures of ammonium sulfate and sulfuric acid across a range of acidities(PH = 0.5 – 2.5) and gas-phase IEPOX into the chamber to generate SOA. The SOA particles were then sent to an oxidation flow reactor, and exposed to different OH concentrations representative of aging of a number of days. We kept relative humidity (RH) constant at ~65%, the temperature was ~23 °C, and levels of oxidation were controlled by adjusting lamp intensity. After oxidized SOA was impacted on quartz substrates, we used single-particle Raman microspectroscopy to identify their functional group compositions. From the Raman vibrational spectra of submicron particles (~500-1000 nm aerodynamic diameter), we observed a distinct difference in core-shell morphology and composition: an organic outer layer and an aqueous-inorganic core. The core also has significantly more CH-stretch than the shell. Small changes were also observed with increasing oxidation, which are important to consider when predicting SOA particle evolution in the atmosphere.more » « less
-
Abstract We recently demonstrated that the heterogeneous hydroxyl radical (·OH) oxidation is an important aging process for isoprene epoxydiol-derived secondary organic aerosol (IEPOX-SOA) that alters its chemical composition, and thus, aerosol physicochemical properties. Notably, dimeric species in IEPOX-SOA were found to heterogeneously react with ·OH at a much faster rate than monomers, suggesting that the initial oligomeric content of freshly-generated IEPOX-SOA particles may affect its subsequent atmospheric oxidation. Aerosol acidity could in principle influence this aging process by enhancing the formation of sulfated and non-sulfated oligomers in freshly-generated IEPOX-SOA. Many multifunctional organosulfate (OS) products derived from heterogeneous ·OH oxidation of sulfur-containing IEPOX-SOA have been observed in cloud water residues and ice nucleating particles and could affect the ability of aged IEPOX-SOA particles to act as cloud condensation nuclei. Hence, this study systematically investigated the effect of aerosol acidity on the kinetics and products resulting from heterogeneous ·OH oxidation of IEPOX-SOA particles. Gas-phase IEPOX was reacted with inorganic sulfate particles of varying pH (0.5 to 2.0) in an indoor smog chamber operated under dark, steady-state conditions to form freshly-generated IEPOX-SOA particles. These particles were then aged at a relative humidity of 60% in an oxidation flow reactor (OFR) for 0-15 days of equivalent atmospheric ·OH exposure. Aged IEPOX-SOA particles were sampled by an online aerosol chemical speciation monitor (ACSM) to measure real-time aerosol mass and chemical changes of the SOA particles, and were also collected onto Teflon filters and into PILS vials for molecular-level chemical analyses by hydrophilic liquid interaction chromatography method interfaced to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (HILIC/ESI-HR-QTOFMS), ion chromatography, and total OS mass amounts.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1038/s41467-020-18424-6
