Solvent and cosolute dependence of Mg surface enrichment in submicron aerosol particles

The formation of multicomponent aerosol particles from precursor solution droplets often involves segregation and surface enrichment of the different solutes, resulting in non-homogeneous particle structures and diverse morphologies. In particular,...

Online Chemical Characterization and Sources of Submicron Aerosol in the Major Mediterranean Port City of Piraeus, Greece

Port cities are affected by a wide array of emissions, including those from the shipping, road transport, and residential sectors; therefore, the characterization and apportionment of such sources in a high temporal resolution is crucial. This study presents measurements of fine aerosol chemical composition in Piraeus, one of the largest European ports, during two monthly periods (winter vs. summer) in 2018–2019, using online instrumentation (Aerosol Chemical Speciation Monitor—ACSM, 7-λ aethalometer). PMF source apportionment was performed on the ACSM mass spectra to quantify organic aerosol (OA) components, while equivalent black carbon (BC) was decomposed to its fossil fuel combustion and biomass burning (BB) fractions. The combined traffic, shipping and, especially, residential emissions led to considerably elevated submicron aerosol levels (22.8 μg m−3) in winter, which frequently became episodic late at night under stagnant conditions. Carbonaceous compounds comprised the major portion of this submicron aerosol in winter, with mean OA and BC contributions of 61% (13.9 μg m−3) and 16% (3.7 μg m−3), respectively. The contribution of BB to BC concentrations was considerable and spatially uniform. OA related to BB emissions (fresh and processed) and hydrocarbon-like OA (from vehicular traffic and port-related fossil fuel emissions including shipping) accounted for 37% and 30% of OA, respectively. In summer, the average PM1 concentration was significantly lower (14.8 μg m−3) and less variable, especially for the components associated with secondary aerosols (such as OA and sulfate). The effect of the port sector was evident in summer and maintained BC concentrations at high levels (2.8 μg m−3), despite the absence of BB and improved atmospheric dispersion. Oxygenated components yielded over 70% of OA in summer, with the more oxidized secondary component of regional origin being dominant (41%) despite the intensity of local sources, in the Piraeus environment. In general, with respect to local sources that can be the target of mitigation policies, this work highlights the importance of port-related activities but also reveals the extensive wintertime impact of residential wood burning. While a separation of the BB source is feasible, more research is needed on how to disentangle the short-term effects of different fossil-fuel combustion sources.

Sizing response of the Ultra-High Sensitivity Aerosol Spectrometer (UHSAS) and Laser Aerosol Spectrometer (LAS) to changes in submicron aerosol composition and refractive index

We evaluate the sensitivity of the size calibrations of two commercially available, high-resolution optical particle sizers to changes in aerosol composition and complex refractive index (RI). The Droplet Measurement Technologies Ultra-High Sensitivity Aerosol Spectrometer (UHSAS) and the TSI, Inc. Laser Aerosol Spectrometer (LAS) are two commonly used instruments for measuring the portion of the aerosol size distribution with diameters larger than nominally 60–90 nm. Both instruments illuminate particles with a laser and relate the single-particle light scattering intensity and count rate measured over a wide range of angles to the size-dependent particle concentration. While the optical block geometry and flow system are similar for each instrument, a significant difference between the two models is the laser wavelength (1054 nm for the UHSAS and 633 nm for the LAS) and intensity (about 100 times higher for the UHSAS), which may affect the way each instrument sizes non-spherical or absorbing aerosols. Here, we challenge the UHSAS and LAS with laboratory-generated, mobility-size-classified aerosols of known chemical composition to quantify changes in the optical size response relative to that of ammonium sulfate (RI of 1.52+0i at 532 nm) and NIST-traceable polystyrene latex spheres (PSLs with RI of 1.59+0i at 589 nm). Aerosol inorganic salt species are chosen to cover the real refractive index range of 1.32 to 1.78, while chosen light-absorbing carbonaceous aerosols include fullerene soot, nigrosine dye, humic acid, and fulvic acid standards. The instrument response is generally in good agreement with the electrical mobility diameter. However, large undersizing deviations are observed for the low-refractive-index fluoride salts and the strongly absorbing nigrosine dye and fullerene soot particles. Polydisperse size distributions for both fresh and aged wildfire smoke aerosols from the recent Fire Influence on Regional to Global Environments Experiment and Air Quality (FIREX-AQ) and the Cloud, Aerosol, and Monsoon Processes Philippines Experiment (CAMP2Ex) airborne campaigns show good agreement between both optical sizers and contemporaneous electrical mobility sizing and particle time-of-flight mass spectrometric measurements. We assess the instrument uncertainties by interpolating the laboratory response curves using previously reported RIs and size distributions for multiple aerosol type classifications. These results suggest that, while the optical sizers may underperform for strongly absorbing laboratory compounds and fresh tailpipe emissions measurements, sampling aerosols within the atmospherically relevant range of refractive indices are likely to be sized to better than ±10 %–20 % uncertainty over the submicron aerosol size range when using instruments calibrated with ammonium sulfate.