Differences between tailpipe and dilution tunnel sub-23 nm nonvolatile (solid) particle number measurements

European Union vehicle and engine regulations require measurement of nonvolatile (solid) particles with diameter >23?nm at the dilution tunnel. In 2019 it was decided to include particles >10?nm in the post Euro 6/VI regulations. Recent studies showed that sub-23?nm measurements are not only susceptible to volatile artifacts (i.e., re-nucleation downstream of the evaporation tube of the particle number system) but also to nonvolatile artifacts (i.e., nonvolatile particles formed in the tubing between the vehicle and the particle number system or in the particle number system itself). In order to investigate the origin of the nonvolatile particle formation, steady-state tests with a moped, a compressed natural gas (CNG), and a diesel vehicle while regenerating were conducted. Systems at the tailpipe and the dilution tunnel with evaporation tubes or catalytic strippers and condensation particle counters (CPCs) with 50% detection efficiencies at 2.5?nm, 4?nm, 10?nm, and 23?nm were used. The results showed higher concentrations of sub-23?nm particles at the dilution tunnel than at the tailpipe when facility preconditioning was not appropriate, the exhaust gas temperature exceeded 300?°C, and high concentrations of semi-volatile material were emitted (e.g., regenerations, lubricant oil).     

A diethylene glycol condensation particle counter for rapid sizing of sub-3 nm atmospheric clusters

Abstract

This article describes the modification of a laminar flow, thermally diffusive universal-fluid condensation particle counter (standard operation: 50% detection efficiency at 5?nm) to rapidly measure the size distribution of sub 3?nm aerosol. Sub 3?nm detection was achieved by using diethylene glycol as the working fluid, which enabled high instrument super-saturations while minimizing homogenous nucleation of the working fluid; a detection efficiency of 50% was achieved at 1.6?nm with laboratory-generated ammonium sulfate (AS) aerosol. Rapid aerosol sizing beneath 3?nm was achieved by inverting the measured grown droplet size distribution (1?s sampling) to recover the sampled aerosol size distribution. The developed inversion algorithm utilizes analytical kernel functions determined from the instrument response to pseudo-monodisperse AS aerosol from 1.5?nm to 20?nm, generated by a high-resolution DMA and a nano DMA. The inversion algorithm was tested numerically with assumed, idealized aerosol size distributions consistent with observed new particle formation events, yielding a reasonable agreement between inverted and assumed aerosol size distributions below 3?nm. This technique provides a measure of the aerosol size assuming an aerosol composition identical to that of the aerosol used to generate the experimentally determined kernel function.

Copyright © 2018 American Association for Aerosol Research     

Review of sub-3 nm condensation particle counters,calibrations, and cluster generation methods

This review discusses the developments in aerosol instrumentation that have led to the current vapor condensation based instruments capable of detecting sub-3?nm particles. We begin from selected reports prior to the year 1991, which have advanced the technology or understanding in condensation particle counting toward sub-3?nm sizes, and continue to more in depth review of the past efforts after 1991. We discuss how the developments in the calibration methods have progressed the development of particle counting techniques, and review briefly the sub-3?nm calibration experiments and cluster production methods used in calibration experiments. Based on these reviews, we identify several technological and scientific advances for the future to improve the accuracy, understanding, and technology of sub-3?nm particle counting.

Copyright © 2019 American Association for Aerosol Research     

Investigation of Absorption and Scattering Properties of Soot Aggregates of Different Fractal Dimension at 532 nm Using RDG and GMM

Radiative properties of numerically generated fractal soot aggregates of different fractal dimensions were studied using the numerically accurate generalized Mie-solution method (GMM) and the Rayleigh-Debye-Gans (RDG) approximate theory. Fractal aggregates of identical prefactor but different fractal dimensions, namely, 1.4, 1.78, and 2.1, were generated numerically using a tunable algorithm of cluster–cluster aggregation for aggregates containing up to 800 primary particles. Radiative properties of these aggregates were calculated at a wavelength of 532 nm assuming a soot refractive index of 1.6 + 0.6i. Four commonly used structure factors in the RDG approximation were used to investigate the effect of structure factor on the differential and total scattering cross-sections and the asymmetry factor. The differential and total scattering properties calculated using the RDG approximation become increasingly sensitive to the structure factor with increasing the fractal dimension. Primary particle interactions are the fundamental mechanism for the aggregate absorption enhancement for small aggregates and the shielding effect for larger aggregates. The extent of these two competing factors is dependent on the fractal dimension and aggregate size. RDG reasonably predicts the effect of fractal dimension on the scattering properties, but fails to account for the effect of aggregation or fractal morphology on the absorption property of fractal soot aggregates, though the error is in general less than 15%.

Copyright 2013 American Association for Aerosol Research     

Mobility Analysis of 2 nm to 11 nm Aerosol Particles with an Aspirating Drift Tube Ion Mobility Spectrometer

We describe the performance of a drift tube-ion mobility spectrometry (DT-IMS) instrument for the measurement of aerosol particles. In DT-IMS, the electrical mobility of a measured particle is inferred directly from the time required for the particle to traverse a drift region, with motion driven by an electrostatic field. Electrical mobility distributions are hence linked to arrival time distributions (ATDs) for particles reaching a detector downstream of the drift region. The developed instrument addresses two obstacles that have limited DT-IMS use for aerosol measurement previously: (1) conventional drift tubes cannot efficiently sample charged particles at ground potential and (2) the sensitivities of commonly used Faraday plate detectors are too low for most aerosols. Obstacle (1) is circumvented by creating a “sample volume” of aerosol for measurement, defined by the streamlines of fluid flow. Obstacle (2) is bypassed by interfacing the end of the drift region with a condensation particle counter. The DT-IMS prototype shows high linearity for arrival time versus inverse electrical mobility (R ² > 0.99) over the size range tested (2.2–11.1 nm), and measurements compare well with both analytical and numerical models of device performance. A dimensionless calibration curve linking drift time to inverse electrical mobility is developed. In less than 5 s, it is possible to measure 11.1 nm particles, while 2.2 nm particles are analyzable on a subsecond scale. The transmission efficiency is found to be dependent upon electrostatic deposition for short drift times and upon advective losses for long drift times.

Copyright 2014 American Association for Aerosol Research     

Laboratory measurements of light scattering properties of kaolinite dust at 532 nm

Light scattering by kaolinite dust samples at 532 nm is studied using a newly developed laboratory apparatus. During the experiments, dust samples are suspended in water, aerosolized by a nebulizer, and then injected into the scattering zone, with or without going through a diffusion drier, to generate either dried dust particles or water droplets with dust inclusions. The light source is a dual wavelength (532 and 1064 nm) diode-pumped solid state laser. Light scattered by an ensemble of particles is collected by a charge-coupled device (CCD) camera, which is mounted on the rotating arm of a stepper motor. The stepper motor rotates the CCD to cover the scattering angle range from 3° to 177°. Polarized scattering light is measured for the horizontally and vertically polarized incident light. The apparatus is calibrated, using pure water droplets as the scattering media. The response function with respect to the scattering angle is obtained by comparing the measurements with Lorenz–Mie calculations and then used in the later data analysis. Measurements show that the backward scattering features of the water droplets are smoothened due to their dust inclusions. Numerical simulations and measurements are extensively compared and discussed. It is found that the Lorenz–Mie theory is inadequate to reproduce the scattering phase functions of either dust particles or water droplets with dust inclusions. A nonspherical aggregate model is applied to simulate the scattering phase functions. The simulation is able to reproduce the overall scattering features; however, substantial discrepancies still exist due to uncertainties in particle shape and refractive index.

Copyright © 2018 American Association for Aerosol Research     

The Ultrasonic Investigation of Phase Transition in Olive Oil up to 0.7 GPa

This paper presents measurements of sound velocity and attenuation in olive oil, with known chemical composition, as a function of pressure, within the range of pressure up to 0.7 GPa. Dependencies of sound velocity, relative ultrasonic wave attenuation, volume, and adiabatic compressibility on pressure show discontinuities. This proves the existence of the first order phase transition in olive oil (liquid to solid-like phase transition). Rapid and large changes in relative attenuation testify to the existence of a phase transition in olive oil. Moreover, the kinetics of phase transition was also investigated. Measurement of acoustic wave velocity and relative attenuation in olive oil during the phase transition and in the high-pressure phase is a novelty. The results obtained can be useful in the development of new methods in food (edible oils) control, processing, and preservation.     

Penetration of Sub-50 nm Nanoparticles Through Electret HVAC Filters Used in Residence

Pleated electret HVAC filters are often used in residence to mitigate the particles that originate both indoors and outdoors. These filters are usually tested with particles larger than 300 nm. However, residential particles can contain a significant amount of nanoparticles with size below 50 nm due to cooking, smoking, cleaning, wood burning, and outdoor infiltration. In order to characterize the nanoparticle removal by electret HVAC filters, penetrations of 3–50 nm silver nanoparticles through five different flat sheet electret media used in commercial residential HVAC filters were tested with face velocities of 0.05, 0.5, and 1.0 m s^–1. Experimental results showed that all media had significantly high penetrations with 0.35–0.8 at the most penetrating particle sizes (MPPSs) for all three velocities, which were in the sizes of 10–30 nm. A model based on single fiber theory for particle penetration predictions was used and compared with the experimental data. Results showed that the model predicted the nanoparticle penetrations very well for all media and all face velocities tested. According to the model, for enhancing the nanoparticle efficiency of the current commercial HVAC filters, the fiber diameter should be reduced or the number of pleats should be increased. However, by doing these, pressure drop and cost may be largely increased. On the other hand, this study found the existing commercial mechanical HVAC filters were much capable for sub–50 nm nanoparticle removal when their minimum efficiency reporting values (MERVs) were larger than 13 and it is concluded mechanical HVAC filters can do a better job than electret ones. However, the quality factor analysis showed electret filters could be regarded as the best filter media for removing particles smaller than 300 nm.

Copyright 2015 American Association for Aerosol Research     

The efficiency of diffusional particle collection onto wire grids in the mobility equivalent size range of 1.2–8 nm

The diffusional deposition efficiency of monomobile, singly charged nanoaerosols onto electrically grounded metal wire mesh was measured on the basis of electrometer current data. The overall experimental uncertainty was of the order of 1% of measured penetration and 1% of measured particle mobility. The aerosol was either WO_x produced by evaporation/condensation and classified with a special high flow DMA into mobility classes between 1.2 and 8 nm—or electrosprayed THAB ions with a mobility equivalent diameter of 1.44 or 1.76 nm for the monomer and dimer, respectively.The experimental data were compared first to a model by Cheng and Yeh for diffusion deposition onto wire screens. Very good agreement was found down to approximately 3–4 nm, however, with a progressive deviation toward lower than predicted penetration values (predicted by pure diffusion theory (over ?25% at 1.2 nm)). The WO_x data agree very well with penetration data obtained for THAB monomer and dimer. For the larger size range above 4 nm, our data are also in excellent agreement with recent data by Thomas et al. It can be concluded that, no thermal rebound effect exists for charged particles in the electrical mobility diameter size range down to 1.2 nm. Lower than predicted penetrations measured below about 3 nm are most likely due to a small contribution by the image charge effect coupled with diffusion. Comparisons between the electrical and diffusional mobility of THAB ions show that the monomer is split into at least two different electrical mobility peaks, however, with the same diffusion coefficient, thus indicating the possible existence of structural isomers for the THAB monomer.     

Fe-doped LaCoO<Subscript>3</Subscript> perovskite catalyst for NO oxidation in the post-treatment of marine diesel engine’s exhaust emissions

New post-treatment process for marine diesel engine exhaust emissions was proposed by combining NO oxidation and wet scrubbing technology for the simultaneous removal of SO_X, NO_X and PM. NO, insoluble in aqueous scrubbing absorbent, is preferentially oxidized to NO₂, which then turns fully soluble in it. Fe substituted LaCo_1-xFe_xO₃ perovskite catalysts were developed for NO oxidation to NO₂. The catalysts were prepared by co-precipitation method and analyzed with XRD, XRF, BET, FT-IR, NO-TPD and XPS techniques. Crystal structure change from rhombohedral to orthorhombic was observed with the increased amount of Fe substituted in the B site of the perovskite by XRD analysis. From FT-IR and NO-TPD analysis, nitrate on perovskite species was found to be the active species for NO oxidation. Quantitative analysis was performed within the prepared catalysts. Catalytic activity was measured using a packed bed reactor operated at 150–400 °C, atmospheric pressure and with gas hourly space velocity (GHSV) of 20,000 h^-1 using a simulated exhaust gas composed of NO 400 ppm, O₂ 10% balanced with N2. Formation of Fe⁴⁺ cation enhanced the redox property as well as the mobility of the lattice oxygen present in the perovskite catalysts, confirmed by XPS analysis. Reaction mechanism of NO oxidation on Fe substituted LaCo_1-xFe_xO₃ was discussed based on Mars-van Krevelen mechanism.     

Performance of bipolar diffusion chargers: Experiments with particles in the size range of 100 to 900 nm

Accurate measurement of particle size distribution using electrical-mobility techniques requires knowledge of the charging state of the sampled particles. A consistent particle charge distribution is possible with bipolar diffusion chargers operated under steady-state condition. Theoretical steady-state charge distributions for bipolar charging are well established but recent studies have shown that the performance of particle chargers is a strong function of particle size, particle concentration, ion source, and charger operating conditions. Most of these studies have focused on particles smaller than 100 nm and the applicability of these results for particles larger than 100 nm must be investigated. In this study, experimentally obtained singly-charged and doubly-charged fractions are compared against theoretical predictions for particles in the size range of 100 to 900 nm. The experimental results show that the commercial soft X-ray charger performs as theoretically-predicted over the range of conditions studied while the performance of other commonly used radioactive chargers (⁸⁵Kr and ²¹⁰Po) are dependent on source strengths, flowrates, particle charge polarities, and particle sizes. From measurements of particle residence times and ion concentrations in different test bipolar chargers, prior observations of flowrate-dependent charging fractions can be explained. Additionally, the results from this study are used to determine an acceptable time period for usage of the commercial TSI 3077A ⁸⁵Kr chargers for steady-state charging as a function of flowrate.

Copyright © 2018 American Association for Aerosol Research     

Investigation of the anticorrosion efficiency of ferrites Mg1−xZnxFe2O4 with different particle morphology and chemical composition in epoxy-ester resin-based coatings

Mixed metal oxides with the ferrospinel structure ZnFe₂O₄, Mg_0.2Zn_0.8Fe₂O₄ and MgFe₂O₄ were synthesised by the high-temperature solid-phase process. A series of pigments containing the metals Mg–Zn–Fe was prepared from 4 different starting iron oxides: viz. goethite (FeOOH), hematite (Fe₂O₃), magnetite (FeO·Fe₂O₃) and specularite (Fe₂O₃). The properties of the ferrites as pigments were examined in a solvent-based epoxy-ester resin-based coating material at a pigment volume concentration PVC_ferrite = 10%. The anticorrosion efficiency of the paints with the ferrites was examined by exposing panels coated with the paints to atmospheres with SO₂, NaCl, or condensed moisture. Furthermore, the physico-mechanical properties of paint films containing the pigments were evaluated by standardised tests. Ferrites prepared from the needle-shaped FeOOH or lamellar Fe₂O₃ emerged as pigments with the best anticorrosion properties. From the aspect of chemical composition, the paint films containing Mg_0.2Zn_0.8Fe₂O₄, i.e. combinations of the cations Mg–Zn, were assessed as the best.     

Absence of any effect of the electric charging state of particles below 10 nm on their penetration through a metal grid

The effect of image force on the penetration of nanometer particles through metal grids remains a controversial issue. Experimental evidence of the existence and of the absence of such effect have both been reported in the past. A careful experimental work to measure penetration of particles in the mobility equivalent diameter range between 3.4 and 10 nm has been carried out. The possible particle size change between the aerosol generator and the filter has been considered, as well as the possible effect of particle number concentration on the filtration efficiency. The geometric dimensions of the filter allowed attainment of the fully developed parabolic flow velocity profile upstream the grid. Measurements were done at two values of the fiber Reynolds number, 0.09 and 0.12, much smaller than 1, as demanded by the currently accepted filtration theory. Penetration of charged particles, measured in three alternative ways, has been compared with penetration of uncharged and neutral particles (the latter consisting of a mixture of positive, negative, and uncharged particles). Two main conclusions have been reached: (1) the charging state of the particles does not affect their penetration through the metal grid and (2) the experimentally measured penetrations are fairly well predicted by the fan filter model of Cheng and Yeh.

Copyright © 2018 American Association for Aerosol Research     

Ultrafine particles from diesel vehicle emissions at different driving cycles induce differential vascular pro-inflammatory responses: Implication of chemical components and NF-κB signaling

Background

Nanometer silicon dioxide (nano-SiO₂) has a wide variety of applications in material sciences, engineering and medicine; however, the potential cell biological and proteomic effects of nano-SiO₂ exposure and the toxic mechanisms remain far from clear.

Results

Here, we evaluated the effects of amorphous nano-SiO₂ (15-nm, 30-nm SiO₂). on cellular viability, cell cycle, apoptosis and protein expression in HaCaT cells by using biochemical and morphological analysis, two-dimensional differential gel electrophoresis (2D-DIGE) as well as mass spectrometry (MS). We found that the cellular viability of HaCaT cells was significantly decreased in a dose-dependent manner after the treatment of nano-SiO₂ and micro-sized SiO₂ particles. The IC₅₀ value (50% concentration of inhibition) was associated with the size of SiO₂ particles. Exposure to nano-SiO₂ and micro-sized SiO₂ particles also induced apoptosis in HaCaT cells in a dose-dependent manner. Furthermore, the smaller SiO₂ particle size was, the higher apoptotic rate the cells underwent. The proteomic analysis revealed that 16 differentially expressed proteins were induced by SiO₂ exposure, and that the expression levels of the differentially expressed proteins were associated with the particle size. The 16 proteins were identified by MALDI-TOF-TOF-MS analysis and could be classified into 5 categories according to their functions. They include oxidative stress-associated proteins; cytoskeleton-associated proteins; molecular chaperones; energy metabolism-associated proteins; apoptosis and tumor-associated proteins.

Conclusions

These results showed that nano-SiO₂ exposure exerted toxic effects and altered protein expression in HaCaT cells. The data indicated the alterations of the proteins, such as the proteins associated with oxidative stress and apoptosis, could be involved in the toxic mechanisms of nano-SiO₂ exposure.     

Characterization of the TSI model 3086 differential mobility analyzer for classifying aerosols down to 1 nm

Measurement systems for particle sizing starting at 1 nm are used to bridge the gap between mass spectrometer measurements and traditional aerosol sizing methods, and thus to enable measurement of the complete size distribution from molecules and clusters to large particles. Such a measurement can be made using a scanning mobility particle sizer equipped with a diethylene glycol growth engine (e.g., TSI Model 3777 Nano Enhancer) along with a condensation particle counter, and a differential mobility analyzer (DMA) appropriate for such small sizes. Previous researchers have used high-resolution DMA (HRDMA) and also the TSI Nano-DMA (Model 3085) in such a scanning mobility particle sizer system. In this study, we evaluate the performance of the recently introduced TSI 1 nm-DMA (Model 3086). The transfer function was characterized using 1–2 nm monomobile molecular ion standards. The same measurements were repeated on a TSI Nano-DMA, with good agreement to previously published values. From the measured transfer function, the resolution of each DMA model was determined as a function of particle size and sheath flow rate. Resolution of the TSI 3086 in the 1–2 nm range was 10–25% higher than the TSI 3085. Measured resolutions of the TSI 3086 were 10–20% lower than theoretically predicted values, whereas those of the Model 3085 were 0–10% lower.

Copyright © 2018 TSI Inc.     

First measurements of the number size distribution of 1–2 nm aerosol particles released from manufacturing processes in a cleanroom environment

This study was conducted to observe a potential formation and/or release of aerosol particles related to manufacturing processes inside a cleanroom. We introduce a novel technique to monitor airborne sub 2 nm particles in the cleanroom and present results from a measurement campaign during which the total particle number concentration (>1 nm and >7 nm) and the size resolved concentration in the 1 to 2 nm size range were measured. Measurements were carried out in locations where atomic layer deposition (ALD), sputtering, and lithography processes were conducted, with a wide variety of starting materials. During our campaign in the clean room, we observed several time periods when the particle number concentration was 10⁵ cm^?3 in the sub 2 nm size range and 10⁴ cm^?3 in the size class larger than 7 nm in one of the sampling locations. The highest concentrations were related to the maintenance processes of the manufacturing machines, which were conducted regularly in that specific location. Our measurements show that around 500 cm^?3 sub 2 nm particles or clusters were in practice always present in this specific cleanroom, while the concentration of particles larger than 2 nm was less than 2 cm^?3. During active processes, the concentrations of sub 2 nm particles could rise to over 10⁵ cm^?3 due to an active new particle formation. The new particle formation was most likely induced by a combination of the supersaturated vapors, released from the machines, and the very low existing condensation sink, leading to pretty high formation rates J_{1.4 nm} = (9 ± 4) cm^?3 s^?1 and growth rates of particles (GR_{1.1–1.3 nm} = (6 ± 3) nm/h and GR_{1.3–1.8 nm} = (14 ± 3) nm/h).

Copyright © 2017 American Association for Aerosol Research     

Photodegradation of Natural Organic Matter in Water with UV Irradiation at 185 and 254 nm: Importance of Hydrodynamic Conditions on the Decomposition Rate

Abstract

The kinetic investigation of photodegradation of the natural organic matter (NOM) in natural lake water was conducted using two low‐pressure mercury lamps of the same nominal power: a) with suprasil quartz envelope emitting at both wavelengths ?254 nm and 185 nm (hereafter VUV); b) with standard quartz envelope emitting only at 254 nm (hereafter UV). In comparison to the UV process, the addition of 185 nm irradiation (VUV process) increased the degradation rate ten‐fold overall at lower and seventeen‐fold at higher Reynolds numbers, respectively. The hydrodynamic characteristics of the photoreactor are of crucial importance for total energy efficiency for VUV processes.     

Fabrication of self-ordered nanoporous alumina with 500–750 nm interpore distances using hard anodization in phosphoric/oxalic acid mixtures

A hard anodization (HA) technique is employed using different mixtures of phosphoric/oxalic acid for fast fabrication of alumina nanopore arrays in voltages higher than 200 V. The mixtures enable to avoid the breakdown of porous anodic alumina (PAA) in the high voltages. It is revealed for the first time that continuously tunable pore intervals (D_int) from 500 to 750 nm can be controlled by varying the concentrations of oxalic acid at anodization voltages (U_anod) from 230 to 360 V, far beyond the U_anod in the single electrolyte of phosphoric acid or oxalic acid. The ratios of interpore distance, pore diameter and barrier layer thickness to anodization voltage are in the range of conventional HA process for each acid mixture. In this approach, the PAA film growth rate is 26 µm/h, being 7 times larger than that in typical mild anodization.