The pH of aerosol particles remains challenging to measure because of their small size, complex composition, and high acidity. Acidity in aqueous aerosol particles, which are found abundantly in the atmosphere, impacts many chemical processes from reaction rates to cloud formation. Only one technique – pH paper – currently exists for directly determining the pH of aerosol particles, and this is restricted to measuring average acidity for entire particle populations. Other methods for evaluating aerosol pH include filter samples, particle-into-liquid sampling, Raman spectroscopy, organic dyes, and thermodynamic models, but these either operate in a higher pH range or are unable to assess certain chemical species or complexity. Here, we present a new method for determining acidity of individual particles and particle phases using carbon quantum dots as a novel in situ fluorophore. Carbon quantum dots are easily synthesized, shelf stable, and sensitive to pH in the highly acidic regime from pH 0 to pH 3 relevant to ambient aerosol particles. To establish the method, a calibration curve was formed from the ratiometric fluorescence intensity of aerosolized standard solutions with a correlation coefficient ( R 2 ) of 0.99. Additionally, the pH of aerosol particles containing a complex organic mixture (COM) representative of environmental aerosols was also determined, proving the efficacy of using carbon quantum dots as pH-sensitive fluorophores for complex systems. The ability to directly measure aerosol particle and phase acidity in the correct pH range can help parametrize atmospheric models and improve projections for other aerosol properties and their influence on health and climate.
more »
« less
Extending surface enhanced Raman spectroscopy (SERS) of atmospheric aerosol particles to the accumulation mode (150–800 nm)
Due to their small size, measurements of the complex composition of atmospheric aerosol particles and their surfaces are analytically challenging. This is particularly true for microspectroscopic methods, where it can be difficult to optically identify individual particles smaller than the diffraction limit of visible light (∼350 nm) and measure their vibrational modes. Recently, surface enhanced Raman spectroscopy (SERS) has been applied to the study of aerosol particles, allowing for detection and characterization of previously undistinguishable vibrational modes. However, atmospheric particles analyzed via SERS have primarily been >1 μm to date, much larger than the diameter of the most abundant atmospheric aerosols (∼100 nm). To push SERS towards more relevant particle sizes, a simplified approach involving Ag foil substrates was developed. Both ambient particles and several laboratory-generated model aerosol systems (polystyrene latex spheres (PSLs), ammonium sulfate, and sodium nitrate) were investigated to determine SERS enhancements. SERS spectra of monodisperse, model aerosols between 400–800 nm were compared with non-SERS enhanced spectra, yielding average enhancement factors of 10 2 for both inorganic and organic vibrational modes. Additionally, SERS-enabled detection of 150 nm size-selected ambient particles represent the smallest individual aerosol particles analyzed by Raman microspectroscopy to date, and the first time atmospheric particles have been measured at sizes approaching the atmospheric number size distribution mode. SERS-enabled detection and identification of vibrational modes in smaller, more atmospherically-relevant particles has the potential to improve understanding of aerosol composition and surface properties, as well as their impact on heterogeneous and multiphase reactions involving aerosol surfaces.
more »
« less
- Award ID(s):
- 1654149
- NSF-PAR ID:
- 10118787
- Date Published:
- Journal Name:
- Environmental Science: Processes & Impacts
- Volume:
- 20
- Issue:
- 11
- ISSN:
- 2050-7887
- Page Range / eLocation ID:
- 1570 to 1580
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
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 Understanding the chemical and physical properties of particles is an important scientific, engineering, and medical issue that is crucial to air quality, human health, and environmental chemistry. Of special interest are aerosol particles floating in the air for both indoor virus transmission and outdoor atmospheric chemistry. The growth of bio- and organic-aerosol particles in the air is intimately correlated with chemical structures and their reactions in the gas phase at aerosol particle surfaces and in-particle phases. However, direct measurements of chemical structures at aerosol particle surfaces in the air are lacking. Here we demonstrate in situ surface-specific vibrational sum frequency scattering (VSFS) to directly identify chemical structures of molecules at aerosol particle surfaces. Furthermore, our setup allows us to simultaneously probe hyper-Raman scattering (HRS) spectra in the particle phase. We examined polarized VSFS spectra of propionic acid at aerosol particle surfaces and in particle bulk. More importantly, the surface adsorption free energy of propionic acid onto aerosol particles was found to be less negative than that at the air/water interface. These results challenge the long-standing hypothesis that molecular behaviors at the air/water interface are the same as those at aerosol particle surfaces. Our approach opens a new avenue in revealing surface compositions and chemical aging in the formation of secondary organic aerosols in the atmosphere as well as chemical analysis of indoor and outdoor viral aerosol particles.more » « less
-
Surface-enhanced Raman spectroscopy (SERS) has great potential as an analytical technique for environmental analyses. In this study, we fabricated highly porous gold (Au) supraparticles ( i.e. , ∼100 μm diameter agglomerates of primary nano-sized particles) and evaluated their applicability as SERS substrates for the sensitive detection of environmental contaminants. Facile supraparticle fabrication was achieved by evaporating a droplet containing an Au and polystyrene (PS) nanoparticle mixture on a superamphiphobic nanofilament substrate. Porous Au supraparticles were obtained through the removal of the PS phase by calcination at 500 °C. The porosity of the Au supraparticles was readily adjusted by varying the volumetric ratios of Au and PS nanoparticles. Six environmental contaminants (malachite green isothiocyanate, rhodamine B, benzenethiol, atrazine, adenine, and gene segment) were successfully adsorbed to the porous Au supraparticles, and their distinct SERS spectra were obtained. The observed linear dependence of the characteristic Raman peak intensity for each environmental contaminant on its aqueous concentration reveals the quantitative SERS detection capability by porous Au supraparticles. The limit of detection (LOD) for the six environmental contaminants ranged from ∼10 nM to ∼10 μM, which depends on analyte affinity to the porous Au supraparticles and analyte intrinsic Raman cross-sections. The porous Au supraparticles enabled multiplex SERS detection and maintained comparable SERS detection sensitivity in wastewater influent. Overall, we envision that the Au supraparticles can potentially serve as practical and sensitive SERS devices for environmental analysis applications.more » « less
-
Mubarak, Nabisab M. ; Walvekar, Rashmi ; Arshid, Numan ; and Khalid, Mohammad (Ed.)Metal oxides are useful for the detection and sensing of combustible and toxic gases, and for use in lithium batteries and solar cells. The present study focuses on the spectroscopic investigation of commercial and in-house laboratory synthesized tetragonal tin dioxide (SnO2), aimed at studying its physical and chemical properties at nanoscale levels and in bulk. We have investigated the pure powder form and thin films prepared on two different types of substrate, silicon and UV-Quartz, each with five different thicknesses (i.e. 41, 78, 96.5, 373, and 908 nm). Raman spectroscopy with two different laser excitation wavelengths, namely 780 and 532 nm, has been used to investigate the various SnO2 vibrational modes. Thermal effects on the primary vibrational features in the Raman spectra have been studied in the range 30–170 °C. X-ray diffraction (XRD) spectra have been recorded to confirm the rutile structure of tin dioxide and to obtain information on the spherical grain particle size of SnO2 with EDS analysis for the thin film samples. Scanning Electron Microscope (SEM) images have been recorded in order to understand the morphology of the particles of SnO2 at the nanoscale level. In addition, FT-IR spectra have been obtained to study the IR-active vibrational modes for the bulk and thin film samples on the two substrates. Moreover, UV-VIS spectra have been employed to determine the energy band gap for the SnO2 film samples by an efficient process facilitated by a Tauc plot technique utilizing an in-house developed python script.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c8em00276b
