Sampling of microplastics at a materials recovery facility.

Detecting, separating, and characterizing airborne microplastics from other airborne particulates is currently challenging due to the various instrumental constraints and related sample preparation hurdles that must be overcome. The ability to measure these real-world environments is needed to better assess the risks associated with microplastics. To that end, the current study focused on developing a methodology for sampling and characterizing airborne microplastics. Particulate sampling was carried out at a municipal materials recovery facility near a conveyer belt containing sorted plastic materials to collect airborne environmental particles on filters. Nucleopore filters were mounted on Teflon support rings, coated with 100 nm aluminum to reduce the background signal for micro-Raman spectroscopy, and marked with a fiducial pattern using a laser engraver. The fiducial pattern was crucial in identifying samples, relocating particles, and efficiently enabling orthogonal measurements on the same samples. Optimum sampling conditions of 2 h at 25 L/min were determined using light microscopy to evaluate the particle loadings. The filters were then cut into slices which were attached to sections of thin beryllium-copper sheeting for easy transfer of the filter between microscopy platforms. Scanning electron microscopy was used to identify carbon-rich particles. Light microscopy was used to identify colored particles which were also carbon-rich which were then analyzed using micro-Raman spectroscopy to identify specific polymers.

Optical Modeling of Single Asian Dust and Marine Air Particles: A Comparison with Geometric Particle Shapes for Remote Sensing.

We compare the optical properties of various geometric shapes with single atmospheric Asian dust and marine background air particles collected at Mauna Loa Observatory. Three-dimensional representations of the particles were acquired with focused ion-beam (FIB) tomography, which involves FIB milling of individual particles followed by imaging and elemental mapping with scanning electron microscopy. Particles were heterogeneous with mainly dolomite or calcite and a minor amount of iron; marine air particles contained gypsum but no iron. Extinction and backscatter fraction were calculated with the discrete dipole approximation method. Geometric shapes were grouped as ellipsoids (sphere, spheroid, ellipsoid), cuboids (cube, square prism, rectangular prism), and pyramids (tetrahedron, triangular pyramid). Each group represented a progression of shapes with 1, 2, or 3 non-identical axes. Most shapes underestimated particle extinction and overestimated the backscatter fraction. Not surprisingly, extinction and the backscatter fraction of the sphere and cube were furthest from those of the particles. While the 3-axis ellipsoid and rectangular prism were closer dimensionally to the particles, extinction and the backscatter fraction for the 2-axis spheroid and square prism, respectively, were often closer to the particles. The extinction and backscatter fraction for the tetrahedron and triangular pyramid were closer on average to the actual particles than were the other shapes. Tetrahedra have the advantage that parameterization of an aerosol model for remote sensing would not require an aspect ratio distribution. Particle surface roughness invariably decreased the backscatter fraction. While surface roughness typically contributes a minor part to overall scattering, in some cases the larger surface area of the tetrahedron and triangular pyramid sufficiently accounted for enhanced forward scattering of particles from surface roughness.

Analysis and Optical Modeling of Individual Heterogeneous Asian Dust Particles Collected at Mauna Loa Observatory.

We have determined optical properties of heterogeneous particles from aerosol samples collected at Hawaii's Mauna Loa Observatory. Back trajectories, satellite imagery, and composition differences among particles from scanning electron microscopy revealed a subset of particles with dolomite or calcite that likely came from Asia. Using focused ion-beam tomography and the discrete dipole approximation, we show how small amounts of an iron phase (oxide or carbonate), or in one case soot, affected extinction and scattering compared with particles of neat dolomite or calcite. We show how particles exhibit a range scattering values due to varying orientations of the inclusion phases. Extinction efficiencies for the heterogeneous particles with dolomite (3.47) and calcite (3.36) were 19% to 21% lower than extinction for marine background air particles (3.72). Extinction for the Asian dust was, however, generally higher than for the neat particles. Compared to iron carbonate, the presence of an absorbing iron oxide affected scattering in Asian dust particles even at the low oxide concentrations studied here (0.6% to 8.1%). Scattering efficiency decreased by <1% with a 1% increase in hematite but by 2% to 5% with magnetite. Asian dust scattered light strongly forward, but backscattering was 56% larger than for the marine background air particles. Backscattering in the Asian dust was also larger with magnetite than hematite. Single scattering albedo for Asian dust with hematite, magnetite, or soot averaged 0.96 ± 0.06 ( x ¯ ± s , n = 19 ) but was as low as 0.72 with a magnetite mass of 5.8%.

The effects of isoprene and NO x on secondary organic aerosols formed through reversible and irreversible uptake to aerosol water.

Isoprene oxidation produces water-soluble organic gases capable of partitioning to aerosol liquid water. The formation of secondary organic aerosols through such aqueous pathways (aqSOA) can take place either reversibly or irreversibly; however, the split between these fractions in the atmosphere is highly uncertain. The aim of this study was to characterize the reversibility of aqSOA formed from isoprene at a location in the eastern United States under substantial influence from both anthropogenic and biogenic emissions. The reversible and irreversible uptake of water-soluble organic gases to aerosol water was characterized in Baltimore, Maryland, USA, using measurements of particulate water-soluble organic carbon (WSOCp) in alternating dry and ambient configurations. WSOCp evaporation with drying was observed systematically throughout the late spring and summer, indicating reversible aqSOA formation during these times. We show through time lag analyses that WSOCp concentrations, including the WSOCp that evaporates with drying, peak 6 to 11h after isoprene concentrations, with maxima at a time lag of 9h. The absolute reversible aqSOA concentrations, as well as the relative amount of reversible aqSOA, increased with decreasing NO x /isoprene ratios, suggesting that isoprene epoxydiol (IEPOX) or other low-NO x oxidation products may be responsible for these effects. The observed relationships with NO x and isoprene suggest that this process occurs widely in the atmosphere, and is likely more important in other locations characterized by higher isoprene and/or lower NO x levels. This work underscores the importance of accounting for both reversible and irreversible uptake of isoprene oxidation products to aqueous particles.

Effect of heterogeneity and shape on optical properties of urban dust based on three-dimensional modeling of individual particles.

We show the effect of composition heterogeneity and shape on the optical properties of urban dust particles based on the three-dimensional spatial and optical modeling of individual particles. Using scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) and focused ion beam (FIB) tomography, spatial models of particles collected in Los Angeles and Seattle accounted for surface features, inclusions, and voids, as well as overall composition and shape. Using voxel data from the spatial models and the discrete dipole approximation method, we report extinction efficiency, asymmetry parameter, and single-scattering albedo (SSA). Test models of the particles involved (1) the particle's actual morphology as a single homogeneous phase and (2) simple geometric shapes (spheres, cubes, and tetrahedra) depicting composition homogeneity or heterogeneity (with multiple spheres). Test models were compared with a reference model, which included the particle's actual morphology and heterogeneity based on SEM/EDX and FIB tomography. Results show particle shape to be a more important factor for determining extinction efficiency than accounting for individual phases in a particle, regardless of whether absorption or scattering dominated. In addition to homogeneous models with the particles' actual morphology, tetrahedral geometric models provided better extinction accuracy than spherical or cubic models. For iron-containing heterogeneous particles, the asymmetry parameter and SSA varied with the composition of the iron-containing phase, even if the phase was <10% of the particle volume. For particles containing loosely held phases with widely varying refractive indexes (i.e., exhibiting "severe" heterogeneity), only models that account for heterogeneity may sufficiently determine SSA.

Incomplete reactions in nanothermite composites.

Exothermic reactions between oxophilic metals and transition/ post transition metal-oxides have been well documented owing to their fast reaction time scales (≈ 10 µs). This article examines the extent of reaction in nano-aluminum based thermite systems through a forensic inspection of the products formed during reaction. Three nanothermite systems (Al/CuO, Al/Bi2O3 and Al/WO3) were selected owing to their diverse combustion characteristics thereby providing sufficient generality and breadth to the analysis. Microgram quantities of the sample were coated onto a fine platinum wire, which was resistively heated at high heating rates (≈ 105 K/s) to ignite the sample. The subsequent products were captured/quenched very rapidly (≈ 500 µs) in order to preserve the chemistry/morphology during initiation and subsequent reaction and were quantitatively analyzed using electron microscopy (EM), focused ion beam (FIB) cross-sectioning followed by energy dispersive X-ray spectroscopy (EDX). Elemental examination of the cross-section of the quenched particles show oxygen predominantly localized in the regions containing aluminum, implying the occurrence of redox reaction. The Al/CuO system, which has simultaneous gaseous oxygen release and ignition (TIgnition ≈ TOxygen Release ), shows substantially lower oxygen content within the product particles as opposed to Al/Bi2O3 and Al/WO3 thermites, which are postulated to undergo a condensed phase reaction (TIgnition << TOxygen Release ). An effective Al:O composition for the interior section was obtained for all the mixtures, with the smaller particles generally showing higher oxygen content than the larger ones. The observed results were further corroborated with the reaction temperature, obtained using a high-speed spectro-pyrometer, and bomb calorimetry conducted on larger samples (≈ 15 mg). The results suggest that thermites that produce sufficient amounts of gaseous products generate smaller product particles and achieve higher extents of completion.

Ammonium addition (and aerosol pH) has a dramatic impact on the volatility and yield of glyoxal secondary organic aerosol.

Glyoxal is an important precursor to secondary organic aerosol (SOA) formed through aqueous chemistry in clouds, fogs, and wet aerosols, yet the gas-particle partitioning of the resulting mixture is not well understood. This work characterizes the volatility behavior of the glyoxal precursor/product mix formed after aqueous hydroxyl radical oxidation and droplet evaporation under cloud-relevant conditions for 10 min, thus aiding the prediction of SOA via this pathway (SOACld). This work uses kinetic modeling for droplet composition, droplet evaporation experiments and temperature-programmed desorption aerosol-chemical ionization mass spectrometer analysis of gas-particle partitioning. An effective vapor pressure (p'L,eff) of ∼10(-7) atm and an enthalpy of vaporization (ΔHvap,eff) of ∼70 kJ/mol were estimated for this mixture. These estimates are similar to those of oxalic acid, which is a major product. Addition of ammonium until the pH reached 7 (with ammonium hydroxide) reduced the p'L,eff to <10(-9) atm and increased the ΔHvap,eff to >80 kJ/mol, at least in part via the formation of ammonium oxalate. pH 7 samples behaved like ammonium oxalate, which has a vapor pressure of ∼10(-11) atm. We conclude that ammonium addition has a large effect on the gas-particle partitioning of the mixture, substantially enhancing the yield of SOACld from glyoxal.