Oil Aerosol Research Articles

Experimental study of the processes of aerosol production for technical oil cleanup

From the experimental study of mechanism of fine mist formation in oil-flooded screw compressor it has been drawn the conclusion on evaporation of fine aerosol of mineral oil that has been obtained in two ways: on the basis of oil spray with mechanical burner and on the basis of volume condensation of oil vapour in air. The given paper presents experimental facility for the production of mineral oil aerosol and also comparison of the experimentation results with calculations.

Effect of oil aerosols on pre-ignition phenomena

Effect of oil aerosols on pre-ignition phenomena

Amphiphobic Polytetrafluoroethylene Membranes for Efficient Organic Aerosol Removal

Polytetrafluoroethylene (PTFE) membrane is an extensively used air filter, but its oleophilicity leads to severe fouling of the membrane surface due to organic aerosol deposition. Herein, we report the fabrication of a new amphiphobic 1H,1H,2H,2H-perfluorodecyl acrylate (PFDAE)-grafted ZnO@PTFE membrane with enhanced antifouling functionality and high removal efficiency. We use atomic-layer deposition (ALD) to uniformly coat a layer of nanosized ZnO particles onto porous PTFE matrix to increase surface area and then subsequently graft PFDAE with plasma. Consequently, the membrane surface showed both superhydrophobicity and oleophobicity with a water contact angle (WCA) and an oil contact angle (OCA) of 150° and 125°, respectively. The membrane air permeation rate of 513 (m(3) m(-2) h(-1) kPa(-1)) was lower than the pristine membrane rate of 550 (m(3) m(-2) h(-1) kPa(-1)), which indicates the surface modification slightly decreased the membrane air permeation. Significantly, the filtration resistance of this amphiphobic membrane to the oil aerosol system was much lower than the initial one. Moreover, the filter exhibited exceptional organic aerosol removal efficiencies that were greater than 99.5%. These results make the amphiphobic PTFE membranes very promising for organic aerosol-laden air-filtration applications.

Effects of bergamot essential oil aerosol on the autonomic nervous system and emotional state of healthy female humans

Effects of bergamot essential oil aerosol on the autonomic nervous system and emotional state of healthy female humans

The Gillings Sampler – An electrostatic air sampler as an alternative method for aerosol in vitro exposure studies

There is growing interest in studying the toxicity and health risk of exposure to multi-pollutant mixtures found in ambient air, and the U.S. Environmental Protection Agency (EPA) is moving towards setting standards for these types of mixtures. Additionally, the Health Effects Institute’s strategic plan aims to develop and apply next-generation multi-pollutant approaches to understanding the health effects of air pollutants. There’s increasing concern that conventional in vitro exposure methods are not adequate to meet EPA’s strategic plan to demonstrate a direct link between air pollution and health effects. To meet the demand for new in vitro technology that better represents direct air-to-cell inhalation exposures, a new system that exposes cells at the air–liquid interface was developed. This new system, named the Gillings Sampler, is a modified two-stage electrostatic precipitator that provides a viable environment for cultured cells. Polystyrene latex spheres were used to determine deposition efficiencies (38–45%), while microscopy and imaging techniques were used to confirm uniform particle deposition. Negative control A549 cell exposures indicated the sampler can be operated for up to 4h without inducing any significant toxic effects on cells, as measured by lactate dehydrogenase (LDH) and interleukin-8 (IL-8). A novel positive aerosol control exposure method, consisting of a p-tolualdehyde (TOLALD) impregnated mineral oil aerosol (MOA), was developed to test this system. Exposures to the toxic MOA at a 1ng/cm2 dose of TOLALD yielded a reproducible 1.4 and 2-fold increase in LDH and IL-8 mRNA levels over controls. This new system is intended to be used as an alternative research tool for aerosol in vitro exposure studies. While further testing and optimization is still required to produce a “commercially ready” system, it serves as a stepping-stone in the development of cost-effective in vitro technology that can be made accessible to researchers in the near future.

Favre- and Reynolds-averaged velocity measurements: Interpreting PIV and LDA measurements in combustion

Previous studies using particle image velocimetry (PIV) and laser Doppler anemometry (LDA) have raised the question of how these measurements should be compared. This study reports on the difference between Favre-averaged and Reynolds-averaged velocity statistics for a turbulent burner using PIV and LDA for unconditional and conditional velocity measurements. The experimental characterization of flow fields of premixed and stratified methane/air flames is carried out under globally turbulent lean conditions (global equivalence ratio at 0.75), over a range of stratifications and swirl numbers. Unconditioned velocity data was acquired using aluminium oxide to seed the flow field. Conditioned measurements were performed using vegetable oil aerosol as seed, which burns through the flame front, thus allowing only the non-reacting flow velocities to be obtained. A critical comparison of unconditioned velocity profiles measured using both PIV and LDA, including axial, radial, and tangential components is made against conditioned and reconstructed mean velocities at different cross-sections of the flame. The comparison reveals how the differences between the Favre-averaged (unconditioned) and the Reynolds-averaged (conditioned) velocity measurements in the flame brush region can be accounted for using the mean progress of reaction, and highlights the limits of the accuracy and agreement between PIV and LDA measurements.

Superamphiphobic nanofibrous membranes for effective filtration of fine particles

The worldwide demands are rising for an energy-efficient and cost-effective approach that can provide advanced nanofibrous membranes with high filtration performance and superior antifouling properties. Here we report a novel synthesized fluorinated polyurethane (FPU) modified nanofibrous membrane optimized to achieve oil and non-oil aerosol particle filtration. By employing the FPU incorporation, the polyacrylonitrile/polyurethane (PAN/PU) composite membranes were endowed with superhydrophobicity with a water contact angle of 154° and superoleophobicity with an oil contact angle of 151°. Morphology, surface wettability, porous structure, and filtration performance could be manipulated by tuning the solution composition as well as the hierarchical structure. Furthermore, the as-prepared membranes can capture, for the first time, a range of different oil aerosol particles in a single-unit operation, with >99.9% filtration efficiency, by using the combined contribution of fiber diameter and surface roughness acting on the objective particles. Exemplified here by the construction of superamphiphobic nanofibrous membrane, numerous applications of this medium includes high efficiency particulate air filters, ultra-low penetration air filters, and respiratory protection equipment.

Filter Performance Degradation of Electrostatic N95 and P100 Filtering Facepiece Respirators by Dioctyl Phthalate Aerosol Loading

Polydisperse dioctyl phthalate (DOP) aerosols are employed for testing filter penetration with loading of R- and P-series particulate filters for National Institute for Occupational Safety and Health (NIOSH) certification. Penetration for filters must not exceed NIOSH allowed maximum levels during the entire loading of 200 mg DOP indicating no filter degradation. Degradation of respirators loaded with DOP by other aerosols as well as respirators exposed to both oil and non-oil aerosols found in some workplaces is not well studied. To better understand the degradation of respirators with electrostatic filter media, two models of N95 and P100 filtering facepiece respirators (FFRs) were loaded with polydisperse DOP aerosols up to 200 mg as employed for NIOSH certification testing with simultaneous measurement of filter penetration. In parallel experiments, both N95 and P100 FFRs were loaded with 10 to 200 mg DOP and challenged with polydisperse NaCl aerosol employed for NIOSH certification testing as well as monodisperse NaCl aerosol, and filter penetration was measured. Results showed that filter penetration for both N95 models increased with increasing amounts of DOP loading and exceeded NIOSH allowed maximum penetration (5%) by both DOP and NaCl aerosols indicating filter degradation. Monodisperse NaCl aerosols (20–400 nm) gradually increased the penetration and shifted the most penetrating particle size from ~40 nm to larger sizes. In the case of P100 FFRs, DOP aerosol penetration was below 0.03% for up to 200 mg DOP loading as required for NIOSH certification. Interestingly, one of the two P100 FFR models loaded with 10–50 mg DOP showed >0.03% penetration with polydisperse, as well as monodisperse, NaCl aerosol testing. Overall, the results obtained in the study indicate that some P100 models loaded with DOP at lower amounts may show higher penetration with other aerosols such as NaCl. Further studies are needed to better understand the filter degradation of DOP loaded respirators.

Intermediate Air Filters for General Ventilation Applications: An Experimental Evaluation of Various Filtration Efficiency Expressions

Neither the European standard nor the US standard for classification of intermediate class filters comprises testing of filter performance with respect to ultrafine particles (UFPs) or particles of the most penetrating size (MPPS). This could turn out to be a major lack in classification standards since UFPs have been pointed out as a serious health hazard. In this study, fractional efficiencies of eight new full-scale bag filters and twenty-three new filter medium samples were determined. The influence of air velocity and aerosol type was investigated, and correlations between efficiencies for UFPs (EFUFPs), MPPS-sized particles (EFMPPS) and 0.4 μm-sized particles (EF0.4μm) were established. The tested bag filters were challenged by four aerosol types: a neutralized atomized oil aerosol, the same oil aerosol but non-neutralized, a non-neutralized thermally generated oil smoke, and a “natural” indoor aerosol. The tests were carried out at different air velocities through the filter medium, ranging between 0.08 m/s and 0.22 m/s. The relationships that were observed between EFUFPs, EFMPPS, and EF0.4μm appeared to be linear within the observed filtration efficiency ranges. These relationships were similar regardless of the test aerosol type used, but somewhat different for glass fiber filters than for charged synthetic filters. Generally, EFMPPS was 10–20% lower than EF0.4μm. The influence of air velocity variations on the size resolved efficiency was determined. The glass fiber filters showed practically the same fractional efficiencies regardless of whether the test aerosol was neutralized or not. However, the charged synthetic filters showed substantially lower efficiencies when tested with the non-neutralized aerosol compared to the case when the aerosol was neutralized.

Monitoring Motor Vehicle PM Emissions: An Evaluation of Three Portable Low-Cost Aerosol Instruments

The burgeoning diversification of particulate matter (PM) emissions regulations creates the need for aerosol monitors for use in engine development, on-board PM measurement, off-road emissions testing, roadside monitoring, and other applications where conventional instruments are impractical or too costly. This work critically examines from two perspectives the performance of three small, relatively inexpensive devices, the DustTrak, Pegasor Particle Sensor, and Diffusion Size Classifier, in engine exhaust PM measurement. First, results from chassis dynamometer vehicle emissions testing reveal that all three can provide accurate PM data that correlate well with the regulatory methods for PM mass and number, but only when there is little variation in morphology and composition. Second, detailed laboratory characterizations with oil and soot aerosols are reported that elucidate how these devices respond to particle size, morphology, and composition. They show that changes in aerosol properties affect all three monitors, but to a degree that depends on their particular detection method, optical, electrical charging, and charging plus diffusion. The results provide calibration data and describe conditions under which these monitors can reliably record PM emissions from engine exhaust. Copyright 2013 American Association for Aerosol Research

Antiviral activity of tea tree and eucalyptus oil aerosol and vapour

Our previous studies demonstrated high antiviral efficiency of natural disinfectants, i.e. tea tree oil (TTO) and eucalyptus oil (EUO) on the filter surface. The TTO aerosol challenge as disinfectant showed its high antiviral potential. The main aim of this study was to investigate the antiviral activity of TTO and EUO aerosols in range of concentrations against Influenza A virus and E. coli phage M13. It was found that both tested oils aerosols possess strong antiviral action and capable of inactivating model viruses with efficiency of more than 95% within 5–15min of exposure. Additionally, the TTO and EUO vapors were also challenged for their antiviral activity. The use of natural disinfectants like TTO and EUO in aerosol form as well as in vapour phase looks very promising for further development of virus inactivating procedures and technologies for air quality applications.

Gaseous VOCs rapidly modify particulate matter and its biological effects – Part 2: Complex urban VOCs and model PM

Abstract. This is the second study in a three-part study designed to demonstrate dynamic entanglements among gaseous organic compounds (VOCs), particulate matter (PM), and their subsequent potential biological effects. We study these entanglements in increasingly complex VOC and PM mixtures in urban-like conditions in a large outdoor chamber, both in the dark and in sunlight. To the traditional chemical and physical characterizations of gas and PM, we added new measurements of gas-only- and PM-only-biological effects, using cultured human lung cells as model living receptors. These biological effects are assessed here as increases in cellular damage or expressed irritation (i.e., cellular toxic effects) from cells exposed to chamber air relative to cells exposed to clean air. Our exposure systems permit side-by-side, gas-only- and PM-only-exposures from the same air stream containing both gases and PM in equilibria, i.e., there are no extractive operations prior to cell exposure for either gases or PM. In Part 1 (Ebersviller et al., 2012a), we demonstrated the existence of PM "effect modification" (NAS, 2004) for the case of a single gas-phase toxicant and an inherently non-toxic PM (mineral oil aerosol, MOA). That is, in the presence of the single gas-phase toxicant in the dark, the initially non-toxic PM became toxic to lung cells in the PM-only-biological exposure system. In this Part 2 study, we used sunlit-reactive systems to create a large variety of gas-phase toxicants from a complex mixture of oxides of nitrogen and 54 VOCs representative of those measured in US city air. In these mostly day-long experiments, we have designated the period in the dark just after injection (but before sunrise) as the "Fresh" condition and the period in the dark after sunset as the "Aged" condition. These two conditions were used to expose cells and to collect chemical characterization samples. We used the same inherently non-toxic PM from the Part 1 study as the target PM for "effect modification". Fortunately, in the absence of "seed particles", the complex highly-reactive VOC system used does not create any secondary aerosol in situ. All PM present in these tests were, therefore, introduced by injection of MOA to serve as PM-to-be-modified by the gaseous environment. PM addition was only done during dark periods, either before or after the daylight period. The purpose of this design is to test if a non-toxic PM becomes toxic in initially unreacted ("Fresh"), or in reacted ("Aged") complex VOC conditions. To have a complete design, we also tested the effects of clean air and the same VOC conditions, but without introducing any PM. Thus, there were six exposure treatment conditions that were evaluated with the side-by-side, gas-only- and PM-only-effects exposure systems; five separate chamber experiments were performed: two with clean air and three with the complex VOC/NOx mixture. For all of these experiments and exposures, chemical composition data and matching biological effects results for two end-points were compared. Chemical measurements demonstrate the temporal evolution of oxidized species, with a corresponding increase in toxicity observed from exposed cells. The largest increase in gas-phase toxicity was observed in the two "Aged" VOC exposures. The largest increase in particle-phase toxicity was observed in the "Aged" VOC exposure with the addition of PM after sunset. These results are a clear demonstration that the findings from Part 1 can be extended to the complex urban oxidized environment. This further demonstrates that the atmosphere itself cannot be ignored as a source of toxic species when establishing the risks associated with exposure to PM. Because gases and PM are transported and deposited differently within the atmosphere and lungs, these results have significant consequences. In the next (and final) part of the study, testing is further applied to systems with real diesel exhaust, including primary PM from a vehicle operated with different types of diesel fuel.

Gaseous VOCs rapidly modify particulate matter and its biological effects – Part 1: Simple VOCs and model PM

Abstract. This is the first of a three-part study designed to demonstrate dynamic entanglements among gaseous organic compounds (VOC), particulate matter (PM), and their subsequent potential biological effects. We study these entanglements in increasingly complex VOC and PM mixtures in urban-like conditions in a large outdoor chamber. To the traditional chemical and physical characterizations of gas and PM, we added new measurements of biological effects, using cultured human lung cells as model indicators. These biological effects are assessed here as increases in cellular damage or expressed irritation (i.e., cellular toxic effects) from cells exposed to chamber air relative to cells exposed to clean air. The exposure systems permit virtually gas-only- or PM-only-exposures from the same air stream containing both gases and PM in equilibria, i.e., there are no extractive operations prior to cell exposure. Our simple experiments in this part of the study were designed to eliminate many competing atmospheric processes to reduce ambiguity in our results. Simple volatile and semi-volatile organic gases that have inherent cellular toxic properties were tested individually for biological effect in the dark (at constant humidity). Airborne mixtures were then created with each compound to which we added PM that has no inherent cellular toxic properties for another cellular exposure. Acrolein and p-tolualdehyde were used as model VOCs and mineral oil aerosol (MOA) was selected as a surrogate for organic-containing PM. MOA is appropriately complex in composition to represent ambient PM, and exhibits no inherent cellular toxic effects and thus did not contribute any biological detrimental effects on its own. Chemical measurements, combined with the responses of our biological exposures, clearly demonstrate that gas-phase pollutants can modify the composition of PM (and its resulting detrimental effects on lung cells). We observed that, even if the gas-phase pollutants are not considered likely to partition to the condensed phase, the VOC-modified-PM showed significantly more damage and inflammation to lung cells than did the original PM. Because gases and PM are transported and deposited differently within the atmosphere and the lungs, these results have significant consequences for a wide range of people. For example, current US policies for research and regulation of PM do not recognize this "effect modification" phenomena (NAS, 2004). These results present an unambiguous demonstration that – even in these simple mixtures – physical and thermal interactions alone can cause a modification of the distribution of species among the phases of airborne pollution mixtures that can result in a non-toxic phase becoming toxic due to atmospheric thermal processes only. Subsequent work (described in companion papers) extends the simple results reported here to systems with photochemical transformations of complex urban mixtures and to systems with diesel exhaust produced by different fuels.

Gaseous VOCs rapidly modify particulate matter and its biological effects - Part 1: Simple VOCs and model PM.

This is the first of a three-part study designed to demonstrate dynamic entanglements among gaseous organic compounds (VOC), particulate matter (PM), and their subsequent potential biological effects. We study these entanglements in increasingly complex VOC and PM mixtures in urban-like conditions in a large outdoor chamber. To the traditional chemical and physical characterizations of gas and PM, we added new measurements of gas-only- and PM-only-biological effects, using cultured human lung cells as model indicators. These biological effects are assessed here as increases in cellular damage or expressed irritation (i.e., cellular toxic effects) from cells exposed to chamber air relative to cells exposed to clean air. The exposure systems permit gas-only- or PM-only-exposures from the same air stream containing both gases and PM in equilibria, i.e., there are no extractive operations prior to cell exposure.Our simple experiments in this part of the study were designed to eliminate many competing atmospheric processes to reduce ambiguity in our results. Simple volatile and semi-volatile organic gases that have inherent cellular toxic properties were tested individually for biological effect in the dark (at constant humidity). Airborne mixtures were then created with each compound and PM that has no inherent cellular toxic properties for another cellular exposure. Acrolein and p-tolualdehyde were used as model VOCs and mineral oil aerosol (MOA) was selected as a surrogate for organic-containing PM. MOA is appropriately complex in composition to represent ambient PM, and it exhibits no inherent cellular toxic effects and thus did not contribute any biological detrimental effects on its own.Chemical measurements, combined with the responses of our biological exposures, clearly demonstrate that gas-phase pollutants can modify the composition of PM (and its resulting detrimental effects on lung cells) - even if the gas-phase pollutants are not considered likely to partition to the condensed phase: the VOC-modified-PM showed significantly more damage and inflammation to lung cells than did the original PM. Because gases and PM are transported and deposited differently within the atmosphere and the lungs, these results have significant consequences. For example, current US policies for research and regulation of PM do not recognize this "effect modification" phenomena (NAS, 2004).These results present an unambiguous demonstration that - even in these simple mixtures - physical and thermal interactions alone can cause a modification of the distribution of species among the phases of airborne pollution mixtures and can result in a non-toxic phase becoming toxic due to atmospheric thermal processes only. Subsequent work extends the simple results reported here to systems with photochemical transformations of complex urban mixtures and to systems with diesel exhaust produced by different fuels.

Variation in Penetration of Submicrometric Particles Through Electrostatic Filtering Facepieces During Exposure to Paraffin Oil Aerosol

Several studies show the increase of penetration through electrostatic filters during exposure to an aerosol flow, because of particle deposition on filter fibers. We studied the effect of increasing loads of paraffin oil aerosol on the penetration of selected particle sizes through an electrostatic filtering facepiece. FFP2 facepieces were exposed for 8 hr to a flow rate of 95.0 ± 0.5 L/min of polydisperse paraffin aerosol at 20.0 ± 0.5 mg/m3. The penetration of bis(2-ethylhexyl)sebacate (DEHS) monodisperse neutralized aerosols, with selected particle size in the 0.03–0.40 μm range, was measured immediately prior to the start of the paraffin aerosol loading and at 1, 4, and 8 hr after the start of paraffin aerosol loading. Penetration through isopropanol-treated facepieces not oil paraffin loaded was also measured to evaluate facepiece behavior when electrostatic capture mechanisms are practically absent. During exposure to paraffin aerosol, DEHS penetration gradually increased for all aerosol sizes, and the most penetrating particle size (0.05 μm at the beginning of exposure) shifted slightly to larger diameters. After the isopropanol treatment, the higher penetration value was 0.30 μm. In addition to an increased penetration during paraffin loading at a given particle size, the relative degree of increase was greater as the particle size increased. Penetration value measured after 8 hr for 0.03-μm particles was on average 1.6 times the initial value, whereas it was about 8 times for 0.40-μm particles. This behavior, as well evidenced in the measurements of isopropanol-treated facepieces, can be attributed to the increasing action in particle capture of the electrostatic forces (Coulomb and polarization), which depend strictly on the diameter and electrical charge of neutralized aerosol particles. With reference to electrostatic filtering facepieces as personal protective equipment, results suggest the importance of complying with the manufacturer instructions when it is specified that their use has to be restricted to a single shift.

Effect of aerosol loading on breakthrough characteristics of activated charcoal cartridges

Charcoal cartridges are commonly employed to provide protection against a wide range of organic vapors at workplace owing to their excellent adsorption. In practical situations, not only organic vapors but also aerosol particles may exist in the workplace atmosphere. Focusing on aerosol particles, this study aimed to evaluate the effect of aerosol loading on both sorption capacity and breakthrough time of activated charcoal. Polydisperse corn oil aerosols with a mode of 0.2μm and monodisperse acrylic powder of 0.15 and 10μm were generated to load the test activated charcoal separately for conducting vapor sorption experiments. For liquid aerosol loading tests, the sorption capacities reduced by 14%, 38% and 46% and the 10% breakthrough times were shorten by 14%, 28% and 75% after loading 0.06, 0.14 and 0.25g of corn oil aerosols per gram charcoal, respectively. For charcoal loaded with solid aerosols, the sorption capacity remained unchanged whereas the 10% breakthrough times were reduced by 26%, 27% and 35% after loading 0.019, 0.027 and 0.029g of 0.15-μm acrylic powder per gram charcoal, and by 5%, 43% and 44% after loading 0.074, 0.13 and 0.18g of 10-μm acrylic aerosols per gram charcoal, respectively. It was concluded that the breakthrough characteristics were affected by aerosol loading and the sorption capacity of activated charcoal can only be reduced by the loading of liquid aerosols. For the use of gas respirators with activated charcoal cartridges, it should be noted that the service life of the charcoal cartridges could be shortened due to aerosol loading in a work environment, from the perspective of respiratory protection.

Evolution of organic aerosol mass spectra upon heating: implications for OA phase and partitioning behavior

Abstract. Vacuum Ultraviolet (VUV) photoionization mass spectrometry has been used to measure the evolution of chemical composition for two distinct organic aerosol types as they are passed through a thermodenuder at different temperatures. The two organic aerosol types considered are primary lubricating oil (LO) aerosol and secondary aerosol from the α-pinene + O3 reaction (αP). The evolution of the VUV mass spectra for the two aerosol types with temperature are observed to differ dramatically. For LO particles, the spectra exhibit distinct changes with temperature in which the lower m/z peaks, corresponding to compounds with higher vapor pressures, disappear more rapidly than the high m/z peaks. In contrast, the αP aerosol spectrum is essentially unchanged by temperature even though the particles experience significant mass loss due to evaporation. The variations in the LO spectra are found to be quantitatively in agreement with expectations from absorptive partitioning theory whereas the αP spectra suggest that the evaporation of αP derived aerosol appears to not be governed by partitioning theory. We postulate that this difference arises from diffusivity within the αP particles being sufficiently slow that they do not exhibit the expected liquid-like behavior and perhaps exist in a glassy state. To reconcile these observations with decades of aerosol growth measurements, which indicate that OA formation is described by equilibrium partitioning, we present a conceptual model wherein the secondary OA is formed and then rapidly converted from an absorbing form to a non-absorbing form. The results suggest that, although OA growth may be describable by equilibrium partitioning theory, the properties of organic aerosol once formed may differ significantly from the properties determined in the equilibrium framework.

EXPERIMENTAL INVESTIGATION OF THE PHENOMENON OF OIL BREAKUP IN AN ENGINE CRANKCASE

A phenomenological study of the characteristics of a two-phase, oil and air mixture was undertaken in a combustion engine crankcase model at speeds of up to 6000 rpm. The idealized model comprised production components and tolerances. Nonintrusive measurement techniques, such as PIV and PDA and high-speed photography, were applied to the study of the oil aerosol and liquid films. Agitated oil pools and impingement on the crankcase surfaces contributed to the aeration of oil in the sump due to windage effects. A mean, wakelike, flow pattern was observed that lagged the crankshaft rotation. Harmonic frequencies were recorded that could be identified with the passage of the position of the maximum crank profile radii and a delay time related to the involute-shaped cord and droplet trajectories induced by drag forces. Highly unsteady flow conditions were measured close to the chamber walls. Three classical breakup modes were identified over three speed ranges. Sheet, ligament, and droplet breakup were observed in the ranges of idle to 1800, 4200, and 6000 rpm. Classification of the particle size distribution for the break-up modes was carried out using the PDA technique. Droplet diameter and velocity data varied in the ranges of 2 μm (dmin) to 130 μm (dmax) and 0−40 ms−1 at 6000 rpm. The ratio of the droplet diameter, dmin;max to a characteristic diameter D at which the oil was observed to break away was compared to the disk Bond number, BoD. For the largest measured droplets, the ratio was approximated by dmax/D = 1.30BoD−0.33 . The disk Bond number was 2.21, while the empirical constant was in the range of 1.82−2.39. The result showed that an appropriate correction must be applied to the universal power law, proposed by Simpkins in 1997 for the estimate of the primary droplet size generated by a spinning disk homogenous atomizer, which had overpredicted the droplet sizes in the case of the crankshaft.

Effective Rate Constants and Uptake Coefficients for the Reactions of Organic Molecular Markers (n-Alkanes, Hopanes, and Steranes) in Motor Oil and Diesel Primary Organic Aerosols with Hydroxyl Radicals

Hydroxyl radical (OH) uptake by organic aerosols, followed by heterogeneous oxidation, happens nearly at the collision frequency. Oxidation complicates the use of organic molecular markers such as hopanes for source apportionment, since receptor models assume markers are stable during transport. We report the oxidation kinetics of organic molecular markers (C(25)-C(32) n-alkanes, hopanes and steranes) in motor oil and primary organic aerosol emitted from a diesel engine at atmospherically relevant conditions inside a smog chamber. A thermal desorption aerosol gas chromatograph/mass spectrometer (TAG) and Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) were used to measure the changes in molecular comosition and bulk primary organic aerosol. From the measured changes in molecular composition, we calculated effective OH rate constants, effective relative rate constants, and effective uptake coefficients for molecular markers. Oxidation rates varied with marker volatility, with more volatile markers being oxidized at rates much faster than could be explained from heterogeneous oxidation. This rapid oxidation can be explained by significant gas-phase OH oxidation that dominates heterogeneous oxidation, resulting in overall oxidation lifetimes of 1 day or less. Based on our results, neglecting oxidation of molecular markers used for source apportionment could introduce significant error, since many common markers such as norhopane appear to be semivolatile under atmospheric conditions.

Constraining the Volatility Distribution and Gas-Particle Partitioning of Combustion Aerosols Using Isothermal Dilution and Thermodenuder Measurements

The gas-particle partitioning of primary organic aerosol (POA) emissions from a diesel engine and the combustion of hard- and soft-woods in a stove was investigated by isothermally diluting them in a smog chamber or by passing them through a thermodenuder and measuring the extent of evaporation. The experiments were conducted at atmospherically relevant conditions: low concentrations and small temperature perturbations. The partitioning of the POA emissions from both sources varied continuously with changing concentration and temperature. Although the POA emissions are semivolatile, they do not completely evaporate at typical atmospheric conditions. The overall partitioning characteristics of diesel and wood smoke POA are similar, with wood smoke being somewhat less volatile than the diesel exhaust. The gas-particle partitioning of aerosols formed from flash-vaporized engine lubricating oil was also studied; diesel POA is somewhat more volatile than the oil aerosol. The experimental data from the dilution- and thermodenuder-based techniques were fit using absorptive partitioning theory to derive a volatility distribution of the POA emissions from each source. These distributions are suitable for use in chemical transport models that simulate POA concentrations.