Rawad Saleh

Direct measurement of toxicants inhaled by water pipe users in the natural environment using a real-time in situ sampling technique.

While narghile water pipe smoking has become a global phenomenon, knowledge regarding its toxicant content and delivery, addictive properties, and health consequences is sorely lagging. One challenge in measuring toxicant content of the smoke in the laboratory is the large number of simplifying assumptions that must be made to model a “typical” smoking session using a smoking machine, resulting in uncertainty over the obtained toxicant yields. In this study, we develop an alternative approach in which smoke generated by a human water pipe user is sampled directly during the smoking session. The method, dubbed real-time in situ sampling (RINS), required developing a self-powered portable instrument capable of automatically sampling a fixed fraction of the smoke generated by the user. Instrument performance was validated in the laboratory, and the instrument was deployed in a field study involving 43 ad libitum water pipe use sessions in Beirut area cafés in which we measured inhaled nicotine, carbon monoxide (CO), and water pipe ma’ssel-derived “tar.” We found that users drew a mean of 119 L of smoke containing 150 mg of CO, 4 mg of nicotine, and 602 mg of ma’ssel-derived “tar” during a single use session (mean duration = 61 min). These first direct measurements of toxicant delivery demonstrate that ordinary water pipe use involves inhaling large quantities of CO, nicotine, and dry particulate matter. Results are compared with those obtained using the Beirut method smoking machine protocol.

Volatility of Organic Molecular Markers Used for Source Apportionment Analysis: Measurements and Implications for Atmospheric Lifetime

Molecular markers are organic species used to define fingerprints for source apportionment of ambient fine particulate matter. Traditionally, these markers have been assumed to be stable in the atmosphere. This work investigates the gas-particle partitioning of eight organic species used as molecular markers in receptor models for biomass burning (levoglucosan), motor vehicles (5α-cholestane, n-hexacosane, n-triacontane, 1,2-benz[a]anthracene, coronene), and meat cooking (cholesterol, oleic acid). Experiments were conducted using a thermodenuder to measure the evaporation of single component particles. The data were analyzed using the integrated volume method to determine saturation concentrations and enthalpies of vaporization for each compound. The results indicate that appreciable quantities (>10%) of most of these markers exist in the gas phase under typical atmospheric conditions. Therefore, these species should be considered semivolatile. Predictions from a chemical kinetics model indicate that gas-particle partitioning has important effects on the atmospheric lifetime of these species. The atmospheric decay of semivolatile compounds proceeds much more rapidly than nonvolatile compounds because gas-phase oxidation induces evaporation of particle-phase material. Therefore, both gas-particle partitioning and chemical reactions need to be accounted for when semivolatile molecular markers are used for source apportionment studies.

Organic aerosol mixing observed by single-particle mass spectrometry.

We present direct measurements of mixing between separately prepared organic aerosol populations in a smog chamber using single-particle mass spectra from the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Docosane and docosane-d46 (22 carbon linear solid alkane) did not show any signs of mixing, but squalane and squalane-d62 (30 carbon branched liquid alkane) mixed on the time scale expected from a condensational-mixing model. Docosane and docosane-d46 were driven to mix when the chamber temperature was elevated above the melting point for docosane. Docosane vapors were shown to mix into squalane-d62, but not the other way around. These results are consistent with low diffusivity in the solid phase of docosane particles. We performed mixing experiments on secondary organic aerosol (SOA) surrogate systems finding that SOA derived from toluene-d8 (a surrogate for anthropogenic SOA (aSOA)) does not mix into squalane (a surrogate for hydrophobic primary organic aerosol (POA)) but does mix into SOA derived from α-pinene (biogenic SOA (bSOA) surrogate). For the aSOA/POA, the volatility of either aerosol does not limit gas-phase diffusion, indicating that the two particle populations do not mix simply because they are immiscible. In the aSOA/bSOA system, the presence of toluene-d8-derived SOA molecules in the α-pinene-derived SOA provides evidence that the diffusion coefficient in α-pinene-derived SOA is high enough for mixing on the time scale of 1 min. The observations from all of these mixing experiments are generally invisible to bulk aerosol composition measurements but are made possible with single-particle composition data.

Elevated toxicant yields with narghile waterpipes smoked using a plastic hose.

The effect of hose permeability on toxicant yields for the narghile waterpipe is investigated, with special reference to the recent adoption of plastic as a hose construction material. Measurements of air infiltration rates for 23 leather and plastic hoses representing 11 types commonly available in Beirut, Lebanon were made, revealing that while leather hoses allowed significant outside air infiltration during a puff constituting up to 31% of the puff volume, plastic hoses were found to be air-tight, indicating that the smoke reaching the waterpipe user can be considerably more concentrated when delivered via a plastic hose. Total particulate matter (TPM), nicotine and carbon monoxide (CO) yields were compared when a waterpipe was machine smoked using a highly permeable leather and an air-tight plastic hose. It was found that the plastic hose resulted in similar yields of nicotine, but more than double the CO yielded with the highly permeable leather hose. Thus, even if narghile smokers titrate for nicotine intake, the use of a plastic hose will likely greatly increase the exposure to CO, a major causative agent in cardiovascular disease.

Contribution of brown carbon and lensing to the direct radiative effect of carbonaceous aerosols from biomass and biofuel burning emissions

We present global direct radiative effect (DRE) calculations of carbonaceous aerosols emitted from biomass/biofuel burning addressing the interplay between two poorly constrained contributions to DRE: mixing state of black carbon (lensing) and light absorption by organic aerosol (OA) due to the presence of brown carbon (BrC). We use the parameterization of Saleh et al. (2014) which captures the variability in biomass/biofuel OA absorption. The global mean effect of OA absorption is +0.22 W/m2 and +0.12 W/m2 for externally and internally mixed cases, while the effect of lensing is +0.39 W/m2 and +0.29 W/m2 for nonabsorbing and absorbing OA cases, signifying the nonlinear interplay between OA absorption and lensing. These two effects can be overestimated if not treated simultaneously in radiative transfer calculations. The combined effect of OA absorption and lensing increases the global mean DRE of biomass/biofuel aerosols from −0.46 W/m2 to +0.05 W/m2 and appears to reduce the gap between existing model-based and observationally constrained DRE estimates. We observed a strong sensitivity to these parameters in key regions, where DRE shifts from strongly negative (  +1 W/m2) when accounting for lensing and OA absorption.

Determination of Evaporation Coefficients of Ambient and Laboratory-Generated Semivolatile Organic Aerosols from Phase Equilibration Kinetics in a Thermodenuder

Accurately predicting formation and partitioning of ambient organic aerosols remains a challenge despite decades of sustained effort in this domain. A major source of uncertainty is the poorly characterized volatility of these aerosols. This uncertainty stems in large part from difficulty separating the overlapping effects of aerosol thermodynamic properties and evaporation coefficients in thermodenuder volatility studies. For lack of other information, it is commonly assumed that the evaporation coefficient is unity when interpreting thermodenuder data, leading to potentially large biases in inferred volatility of the sampled aerosol. In this paper, we present a novel thermodenuder-based approach for determining evaporation coefficients of pure compound and complex aerosols without knowledge of their thermodynamic properties. The method involves tracing the normalized dynamic response of an aerosol system to a step change in temperature as it flows through a heated tube. The approach is validated using pure compounds and a mixture of laboratory-generated dicarboxylic acids, and is applied to concentrated ambient aerosols sampled in Beirut, Lebanon. Three valid data sets were obtained from more than 200 h of ambient air sampling during the month of August 2010, yielding values of 0.34, 0.46, and 0.28 for an assumed binary gas diffusion coefficient of 7.8 × 10−6 m2/s at 60°C. Copyright 2012 American Association for Aerosol Research

Comparison of Gasoline Direct-Injection (GDI) and Port Fuel Injection (PFI) Vehicle Emissions: Emission Certification Standards, Cold-Start, Secondary Organic Aerosol Formation Potential, and Potential Climate Impacts

Recent increases in the Corporate Average Fuel Economy standards have led to widespread adoption of vehicles equipped with gasoline direct-injection (GDI) engines. Changes in engine technologies can alter emissions. To quantify these effects, we measured gas- and particle-phase emissions from 82 light-duty gasoline vehicles recruited from the California in-use fleet tested on a chassis dynamometer using the cold-start unified cycle. The fleet included 15 GDI vehicles, including 8 GDIs certified to the most-stringent emissions standard, superultra-low-emission vehicles (SULEV). We quantified the effects of engine technology, emission certification standards, and cold-start on emissions. For vehicles certified to the same emissions standard, there is no statistical difference of regulated gas-phase pollutant emissions between PFIs and GDIs. However, GDIs had, on average, a factor of 2 higher particulate matter (PM) mass emissions than PFIs due to higher elemental carbon (EC) emissions. SULEV certified GDIs have a factor of 2 lower PM mass emissions than GDIs certified as ultralow-emission vehicles (3.0 ± 1.1 versus 6.3 ± 1.1 mg/mi), suggesting improvements in engine design and calibration. Comprehensive organic speciation revealed no statistically significant differences in the composition of the volatile organic compounds emissions between PFI and GDIs, including benzene, toluene, ethylbenzene, and xylenes (BTEX). Therefore, the secondary organic aerosol and ozone formation potential of the exhaust does not depend on engine technology. Cold-start contributes a larger fraction of the total unified cycle emissions for vehicles meeting more-stringent emission standards. Organic gas emissions were the most sensitive to cold-start compared to the other pollutants tested here. There were no statistically significant differences in the effects of cold-start on GDIs and PFIs. For our test fleet, the measured 14.5% decrease in CO2 emissions from GDIs was much greater than the potential climate forcing associated with higher black carbon emissions. Thus, switching from PFI to GDI vehicles will likely lead to a reduction in net global warming.

Characterizing the Spatial Variation of Air Pollutants and the Contributions of High Emitting Vehicles in Pittsburgh, PA

We used a mobile measurement platform to characterize a suite of air pollutants (black carbon (BC), particle-bound polycyclic aromatic hydrocarbons (PB-PAH), benzene, and toluene) in the city of Pittsburgh and surrounding areas. More than 270 h of data were collected from forty-two sites which were selected based on analysis in the geographic information system (GIS). Mobile measurements were performed during three different times of day (mornings, afternoons/evenings, and overnight) in both winter (November 2011 to February 2012) and summer (June 2012 to August 2012). Pollutant concentrations were elevated in river valleys by 9% (benzene) to 30% (PB-PAH) relative to upland areas. Traffic had strong impacts on measured pollutants. PB-PAH and BC concentrations at high traffic sites were a factor of 2 and 30% higher than at low traffic sites, respectively. Pollutant concentrations were highest in the morning sessions due to a combination of traffic and meteorological conditions. The highly time-resolved data indicated that elevated pollutant concentrations at high traffic sites were due to short duration plume events associated with high emitting vehicles. High emitting vehicles contributed up to 70% of the near road PB-PAH and 30% of BC; emissions from these vehicles drove substantial spatial variations in BC and PB-PAH concentrations. Many high emitting vehicles were presumably diesel trucks or buses, because plumes were strongly correlated with truck traffic volume. In contrast, PB-PAH and BC in the nonplume background air was weakly correlated with traffic, and their spatial patterns were more influenced by terrain and point source emissions. The spatial variability in contributions of high emitting vehicles suggests that the effect of potential control strategies vary for different pollutants and environments.

Effect of Aerosol Generation Method on Measured Saturation Pressure and Enthalpy of Vaporization for Dicarboxylic Acid Aerosols

To date, most studies of the thermodynamic properties of organic aerosols have utilized test aerosols generated by spray atomization followed by a diffusion drying step. Some evidence points to possible biases in measured thermodynamic properties stemming from the presence of residual solvent (water or alcohol) in the dried aerosol. In the current study we compared measurements of thermodynamic properties of organic aerosols generated by atomization of aqueous solutions to those generated by homogeneous condensation using a modified Sinclair-La Mer generator. In particular, using the Integrated Volume Method (Saleh et al. 2008), we measured and compared the saturation pressure (P sat ) at 298 K and enthalpy of vaporization (ΔH) of C-6 (adipic) and C-9 (azelaic) dicarboxylic acid aerosol generated using these techniques. We found that P sat and ΔH exhibited no statistically significant difference across the tested aerosol generation methods, indicating that any residual solvent carried by the particles had no impact on the measurements. For adipic acid, we obtained P sat of 3.3 × 10−5 (±0.9 × 10−5) Pa and ΔH of 132 (±8) kJ/mol with atomization, and P sat of 4.2 × 10− 5 (±2.2 × 10−5) Pa and ΔH of 126 (±21) kJ/mol with homogeneous condensation; for azelaic acid, we obtained P sat of 1.4 × 10−5 (±0.5 × 10−5) Pa and ΔH of 145 (±15) kJ/mol with atomization, and P sat of 0.9 × 10− 5 (±0.3 × 10− 5) Pa and ΔH of 158 (±17) kJ/mol with homogeneous condensation. In addition, SEM images of the acids generated by the two methods showed no obvious difference in surface morphology.

Probing the Evaporation Dynamics of Mixed SOA/Squalane Particles Using Size-Resolved Composition and Single-Particle Measurements.

An analysis of the formation and evaporation of mixed-particles containing squalane (a surrogate for hydrophobic primary organic aerosol, POA) and secondary organic aerosol (SOA) is presented. In these experiments, one material (D62-squalane or SOA from α-pinene + O3) was prepared first to serve as surface area for condensation of the other, forming the mixed-particles. The mixed-particles were then subjected to a heating-ramp from 22 to 44 °C. We were able to determine that (1) almost all of the SOA mass is comprised of material less volatile than D62-squalane; (2) AMS collection efficiency in these mixed-particle systems can be parametrized as a function of the relative mass fraction of the components; and (3) the vast majority of D62-squalane is able to evaporate from the mixed particles, and does so on the same time scale regardless of the order of preparation. We also performed two-population mixing experiments to directly test whether D62-squalane and SOA from α-pinene + O3 form a single solution or two separate phases. We find that these two OA types are immiscible, which informs our inference of the morphology of the mixed-particles. If the morphology is core-shell and dictated by the order of preparation, these data indicate that squalane is able to diffuse relatively quickly through the SOA shell, implying that there are no major diffusion limitations.