Size, Shape, and Phase of Nanoscale Uric Acid Particles

Uric acid particles are formed due to hyperuricemia, and previous works have focused on understanding the surface forces, crystallization, and growth of micron- and supermicron-sized particles. However, little to no work has furthered our understanding about uric acid nanonuclei that precipitate during the initial stages of kidney stone formation. In this work, we generate nanosized uric acid particles by evaporating saturated solution droplets of uric acid. Furthermore, we quantify the effects of drying rate on the morphology of uric acid nanonuclei. An aerosol droplet drying method generates uric acid nanoparticles in the size range of 20–200 nm from aqueous droplets (1–6 μm). Results show that uric acid nanonuclei are non-spherical with a shape factor value in the range of 1.1–1.4. The shape factor values change with drying rate and indicate that the nanoparticle morphology is greatly affected by drying kinetics. The nanonuclei are amorphous but can grow to form crystalline micron-sized particles. Indeed, a pre-crystallization phase was observed for heterogeneous nucleation of uric acid particles in the size range of a few hundred nanometers. Our findings show that the morphology of uric acid nanonuclei is significantly different from that of crystalline supermicron-sized particles. These new findings imply that the dissolution characteristics, surface properties, elimination, and medical treatment of uric acid nanonuclei formed during the initial stages of nucleation must be reconsidered

Components of Particle Emissions from Light-Duty Spark-Ignition Vehicles with Varying Aromatic Content and Octane Rating in Gasoline

Typical gasoline consists of varying concentrations of aromatic hydrocarbons and octane ratings. However, their impacts on particulate matter (PM) such as black carbon (BC) and water-soluble and insoluble particle compositions are not well-defined. This study tests seven 2012 model year vehicles, which include one port fuel injection (PFI) configured hybrid vehicle, one PFI vehicle, and six gasoline direct injection (GDI) vehicles. Each vehicle was driven on the Unified transient testing cycle (UC) using four different fuels. Three fuels had a constant octane rating of 87 with varied aromatic concentrations at 15%, 25%, and 35%. A fourth fuel with higher octane rating, 91, contained 35% aromatics. BC, PM mass, surface tension, and water-soluble organic mass (WSOM) fractions were measured. The water-insoluble mass (WIM) fraction of the vehicle emissions was estimated. Increasing fuel aromatic content increases BC emission factors (EFs) of transient cycles. BC concentrations were higher for the GDI vehicles than the PFI and hybrid vehicles, suggesting a potential climate impact for increased GDI vehicle production. Vehicle steady-state testing showed that the hygroscopicity of PM emissions at high speeds (70 mph; κ > 1) are much larger than emissions at low speeds (30 mph; κ < 0.1). Iso-paraffin content in the fuels was correlated to the decrease in WSOM emissions. Both aromatic content and vehicle speed increase the amount of hygroscopic material found in particle emissions

Electric Field-Induced Water Condensation Visualized by Vapor-Phase Transmission Electron Microscopy

Understanding the nanoscale water condensation dynamics in strong electric fields is important for improving the atmospheric modeling of cloud dynamics and emerging technologies utilizing electric fields for direct air moisture capture. Here, we use vapor-phase transmission electron microscopy (VPTEM) to directly image nanoscale condensation dynamics of sessile water droplets in electric fields. VPTEM imaging of saturated water vapor stimulated condensation of sessile water nanodroplets that grew to a size of ∼500 nm before evaporating over a time scale of a minute. Simulations showed that electron beam charging of the silicon nitride microfluidic channel windows generated electric fields of ∼108 V/m, which depressed the water vapor pressure and effected rapid nucleation of nanosized liquid water droplets. A mass balance model showed that droplet growth was consistent with electric field-induced condensation, while droplet evaporation was consistent with radiolysis-induced evaporation via conversion of water to hydrogen gas. The model quantified several electron beam–sample interactions and vapor transport properties, showed that electron beam heating was insignificant, and demonstrated that literature values significantly underestimated radiolytic hydrogen production and overestimated water vapor diffusivity. This work demonstrates a method for investigating water condensation in strong electric fields and under supersaturated conditions, which is relevant to vapor–liquid equilibrium in the troposphere. While this work identifies several electron beam–sample interactions that impact condensation dynamics, quantification of these phenomena here is expected to enable delineating these artifacts from the physics of interest and accounting for them when imaging more complex vapor–liquid equilibrium phenomena with VPTEM

Will Aerosol Hygroscopicity Change with Biodiesel, Renewable Diesel Fuels and Emission Control Technologies?

The use of biodiesel and renewable diesel fuels in compression ignition engines and aftertreatment technologies may affect vehicle exhaust emissions. In this study two 2012 light-duty vehicles equipped with direct injection diesel engines, diesel oxidation catalyst (DOC), diesel particulate filter (DPF), and selective catalytic reduction (SCR) were tested on a chassis dynamometer. One vehicle was tested over the Federal Test Procedure (FTP) cycle on seven biodiesel and renewable diesel fuel blends. Both vehicles were exercised over double Environmental Protection Agency (EPA) Highway fuel economy test (HWFET) cycles on ultralow sulfur diesel (ULSD) and a soy-based biodiesel blend to investigate the aerosol hygroscopicity during the regeneration of the DPF. Overall, the apparent hygroscopicity of emissions during nonregeneration events is consistently low (κ < 0.1) for all fuels over the FTP cycle. Aerosol emitted during filter regeneration is significantly more CCN active and hygroscopic; average κ values range from 0.242 to 0.439 and are as high as 0.843. Regardless of fuel, the current classification of “fresh” tailpipe emissions as nonhygroscopic remains true during nonregeneration operation. However, aftertreatment technologies such as DPF, will produce significantly more hygroscopic particles during regeneration. To our knowledge, this is the first study to show a significant enhancement of hygroscopic materials emitted during DPF regeneration of on-road diesel vehicles. As such, the contribution of regeneration emissions from a growing fleet of diesel vehicles will be important

Electric Field-Induced Water Condensation Visualized by Vapor-Phase Transmission Electron Microscopy

Understanding the nanoscale water condensation dynamics in strong electric fields is important for improving the atmospheric modeling of cloud dynamics and emerging technologies utilizing electric fields for direct air moisture capture. Here, we use vapor-phase transmission electron microscopy (VPTEM) to directly image nanoscale condensation dynamics of sessile water droplets in electric fields. VPTEM imaging of saturated water vapor stimulated condensation of sessile water nanodroplets that grew to a size of ∼500 nm before evaporating over a time scale of a minute. Simulations showed that electron beam charging of the silicon nitride microfluidic channel windows generated electric fields of ∼108 V/m, which depressed the water vapor pressure and effected rapid nucleation of nanosized liquid water droplets. A mass balance model showed that droplet growth was consistent with electric field-induced condensation, while droplet evaporation was consistent with radiolysis-induced evaporation via conversion of water to hydrogen gas. The model quantified several electron beam–sample interactions and vapor transport properties, showed that electron beam heating was insignificant, and demonstrated that literature values significantly underestimated radiolytic hydrogen production and overestimated water vapor diffusivity. This work demonstrates a method for investigating water condensation in strong electric fields and under supersaturated conditions, which is relevant to vapor–liquid equilibrium in the troposphere. While this work identifies several electron beam–sample interactions that impact condensation dynamics, quantification of these phenomena here is expected to enable delineating these artifacts from the physics of interest and accounting for them when imaging more complex vapor–liquid equilibrium phenomena with VPTEM

A Unique Online Method to Infer Water-Insoluble Particle Contributions

<div><p>Particle number, size, and composition information is important for constraining aerosol effects on air quality, climate, and health. The composition of particles, especially from vehicular sources, may contain insoluble black carbon (BC) materials that modify particle nucleating properties. In this study, we develop a method to provide quantitative and real-time information on the water-insoluble components found in near-road aerosol sources. A water-based condensation particle counter (W-CPC) and a butanol-based CPC (B-CPC) were used to measure the particle number concentration. Both instruments were coupled with a scanning mobility particle sizer (SMPS) to record the particle number and size data. Real time water-insoluble particle mass was estimated from the difference in particle number concentration between the two CPCs; theoretical water-insoluble mass was calculated from the ideal hygro- scopicity single parameter <b>κ</b>-values. This online method was calibrated with test compounds and then applied to data collected from a field study. Ambient aerosol was sampled from a monitoring station located 15 m from the I-710 freeway in Long Beach, California. The results show that near-roadway emissions contain water-insoluble (BC and non-BC) components. Particle number and BC concentrations increase after changes in wind direction near the freeway on both weekday and weekend measurements. Particles were less hygroscopic (<b>κ</b> ∼ 0.2) before changes in wind direction from downwind to upwind of the freeway (<b>κ</b> > 0.6). Rapid changes in water-solubility can be captured with this technique. By assuming a two-component mixture, the water-insoluble mass fractions were inferred. BC shows a positive correlation with the water-insoluble mass however its presence may not account for the entire water-insoluble mass from the near-roadway source.</p><p>Copyright 2014 American Association for Aerosol Research</p></div

Solubility Considerations for Cloud Condensation Nuclei (CCN) Activity Analysis of Pure and Mixed Black Carbon Species

Black carbon (BC) is an aerosol that is released into the atmosphere due to the incomplete burning of biomass and can affect the climate directly or indirectly. BC commonly mixes with other primary or secondary aerosols to undergo aging, thereby changing its radiative properties and cloud condensation nuclei (CCN) activity. The composition of aged BC species in the atmosphere is difficult to measure with high confidence, so their associated CCN activity can be uncertain. In this work, the CCN activity analysis of BC was performed using laboratory measurements of proxy aged BC species. Vulcan XC72R carbon black was used as the representative of BC, and three structural isomers of benzenedicarboxylic acidphthalic acid (PTA), isophthalic acid (IPTA), and terephthalic acid (TPTA)were mixed with BC to generate three different proxies of aged BC species. Most studies related to CCN activity analysis of BC aerosols use the traditional Köhler theory or an adsorption theory (such as the Frenkel–Halsey–Hill adsorption theory). PTA, IPTA, and TPTA fall in the sparingly water-soluble range and therefore do not fully obey either of the aforementioned theories. Consequently, a novel hybrid activity model (HAM) was used for the CCN activity analysis of the BC mixtures studied in this work. HAM combines the features of adsorption theory via the adsorption isotherm with the features of Köhler theory by incorporating solubility partitioning. The results in this work showed that HAM improves the representation of CCN activity of pure and mixed BC aerosol species with high certainty, evident from generally better goodness of fit, R2 > 0.9. This work implies that the hygroscopicity parameterization based on HAM captures the size-dependent variability in the CCN activity of the pure and aged BC species

Electric Field-Induced Water Condensation Visualized by Vapor-Phase Transmission Electron Microscopy

Understanding the nanoscale water condensation dynamics in strong electric fields is important for improving the atmospheric modeling of cloud dynamics and emerging technologies utilizing electric fields for direct air moisture capture. Here, we use vapor-phase transmission electron microscopy (VPTEM) to directly image nanoscale condensation dynamics of sessile water droplets in electric fields. VPTEM imaging of saturated water vapor stimulated condensation of sessile water nanodroplets that grew to a size of ∼500 nm before evaporating over a time scale of a minute. Simulations showed that electron beam charging of the silicon nitride microfluidic channel windows generated electric fields of ∼108 V/m, which depressed the water vapor pressure and effected rapid nucleation of nanosized liquid water droplets. A mass balance model showed that droplet growth was consistent with electric field-induced condensation, while droplet evaporation was consistent with radiolysis-induced evaporation via conversion of water to hydrogen gas. The model quantified several electron beam–sample interactions and vapor transport properties, showed that electron beam heating was insignificant, and demonstrated that literature values significantly underestimated radiolytic hydrogen production and overestimated water vapor diffusivity. This work demonstrates a method for investigating water condensation in strong electric fields and under supersaturated conditions, which is relevant to vapor–liquid equilibrium in the troposphere. While this work identifies several electron beam–sample interactions that impact condensation dynamics, quantification of these phenomena here is expected to enable delineating these artifacts from the physics of interest and accounting for them when imaging more complex vapor–liquid equilibrium phenomena with VPTEM

Electric Field-Induced Water Condensation Visualized by Vapor-Phase Transmission Electron Microscopy

Understanding the nanoscale water condensation dynamics in strong electric fields is important for improving the atmospheric modeling of cloud dynamics and emerging technologies utilizing electric fields for direct air moisture capture. Here, we use vapor-phase transmission electron microscopy (VPTEM) to directly image nanoscale condensation dynamics of sessile water droplets in electric fields. VPTEM imaging of saturated water vapor stimulated condensation of sessile water nanodroplets that grew to a size of ∼500 nm before evaporating over a time scale of a minute. Simulations showed that electron beam charging of the silicon nitride microfluidic channel windows generated electric fields of ∼108 V/m, which depressed the water vapor pressure and effected rapid nucleation of nanosized liquid water droplets. A mass balance model showed that droplet growth was consistent with electric field-induced condensation, while droplet evaporation was consistent with radiolysis-induced evaporation via conversion of water to hydrogen gas. The model quantified several electron beam–sample interactions and vapor transport properties, showed that electron beam heating was insignificant, and demonstrated that literature values significantly underestimated radiolytic hydrogen production and overestimated water vapor diffusivity. This work demonstrates a method for investigating water condensation in strong electric fields and under supersaturated conditions, which is relevant to vapor–liquid equilibrium in the troposphere. While this work identifies several electron beam–sample interactions that impact condensation dynamics, quantification of these phenomena here is expected to enable delineating these artifacts from the physics of interest and accounting for them when imaging more complex vapor–liquid equilibrium phenomena with VPTEM

Impactor collection efficiencies can modify the uncertainty of multiply charged particles in optical extinction measurements

The complex distribution of particle charge states resulting from neutralization processes by radioactive or soft X-ray charge neutralizers is a well-documented problem in aerosol science. Here, we demonstrate that non-idealities in the collection efficiency of an impactor allows for the transmission of an unexpected population of multiply charged particles by a differential mobility analyzer that can bias optical measurements. The extinction cross sections (Cext) of ammonium sulfate particles were quantified using cavity ring-down spectroscopy and particle counting. Particles were selected by electrical mobility (i.e., a metric of particle size) using a differential mobility analyzer (DMA) or electrical mobility and mass selected by a tandem DMA and aerosol particle mass analyzer (APM), respectively, to elucidate multiple charging artifacts. Measured Cext exhibited statistically significant differences at particle sizes near the impactor cut point implying that these multiply charged particles should not be present and could not be confirmed by parallel size distribution measurements. Additionally, comparison of Cext with Mie theory demonstrates that misclassification of the multiply charged particles can give rise to numerically accurate results. To understand these observations, the collection efficiency (CE) of four impactors from similar electrostatic classifiers was investigated. From these measurements, it was determined that the nominal and actual diameters of the impactors differed by −0.5% (457 μm vs. (455 ± 1) μm, respectively (uncertainty is 1σ standard deviation)) but the average Stk50 (the Stokes number at the cut-point, D50) values differed by ≈ 23% (0.23 vs. 0.18 ± 0.01, respectively). The measured CE as a function of √Stk (a metric of particle aerodynamic size) exhibits a long tail toward higher √Stk values, allowing for transmission of the larger and multiply charged particles observed in the optical measurements. These measurements highlight the utility of using orthogonal, spectroscopic methods to quantify the presence of multiply charged particles.</p