Knowledge of the mechanism of formation, levels and toxicological profiles of the chemical products in the aerosols (i.e., vapor plus particulate phases) of e-cigarettes is needed in order to better inform basic research as well as the general public, regulators, and industry. To date, studies of e-cigarette emissions have mainly focused on chromatographic techniques for quantifying and comparing the levels of selected e-cigarette aerosol components to those found in traditional cigarettes. E-cigarettes heat and aerosolize the solvents propylene glycol (PG) and glycerol (GLY), thereby affording unique product profiles as compared to traditional cigarettes. The chemical literature strongly suggests that there should be more compounds produced by PG and GLY than have been reported in e-cigarette aerosols to date. Herein we report an extensive investigation of the products derived from vaporizing PG and GLY under mild, single puff conditions. This has led to the discovery of several new compounds produced under vaping conditions. Prior reports on e-cigarette toxin production have emphasized temperature as the primary variable in solvent degradation. In the current study, the molecular pathways leading to enhanced PG/GLY reactivity are described, along with the most impactful chemical conditions promoting byproduct production.
Electronic cigarettes enabling enhanced airflow have grown in popularity in recent years. The objective of this study is to show that flow rates modulate the levels of specific aerosol toxicants produced in electronic cigarettes. Flow rates used in various laboratory investigations involving e-cigarettes have varied widely to date, and can thus promote interlaboratory variability in aerosol product profiles. The thermal decomposition of hydroxyacetone and glycolaldehyde is less favorable at lower temperatures, supporting the observations of these products at higher flow rates/lower heating coil temperatures. Higher temperatures promote the formation of acetaldehyde from hydroxyacetone and formaldehyde from both hydroxyacetone and glycolaldehyde. A separate finding is that greater airflow can also expose users to concerning levels of e-liquid solvents. Under the modest conditions studied, propylene glycol aerosol levels are found at above the acceptable inhalation levels defined by NASA, and in range of the generally recognized as safe levels for daily ingestion.
The electronic cigarette solvents propylene glycol and glycerol are known to produce toxic byproducts such as formaldehyde, acetaldehyde and acrolein. However, the aerosol toxin yield depends upon a variety of chemical and physical variables. The formaldehyde hemiacetals derived from these solvents were reported as major electronic cigarette aerosol components by us in 2015. In the study described herein, the formaldehyde hemiacetals were found at higher levels than those of free formaldehyde via an orthogonal sample collection protocol. In addition, the common aldehyde collection methods for electronic cigarettes, such as impingers and sorbent tubes containing DNPH, significantly underestimate the levels of formaldehyde. The reason for this is that formaldehyde hemiacetals follow other reaction pathways, such as the formation of a less reactive full cyclic acetal catalyzed by the acidity of the DNPH solution and the silica. We found that formaldehyde hemiacetals are a considerable fraction of the total formaldehyde produced in electronic cigarette that cannot be determined accurately by DNPH derivatization methods. Although the health effects of the hemiacetals are not yet known, they warrant further investigation.
Recently, we reported the presence of dihydroxyacetone (DHA), the active ingredient in sunless tanners, in the aerosol of an electronic cigarette. DHA has been shown to react with DNA in vitro. The FDA restricts the use of DHA to external application only. It states that it should not be inhaled, ingested, or come into contact with any areas containing mucous membranes, due to unknown risk. Herein, the quantification of DHA in the aerosols of three brands of e-cigarettes has been carried out. These included two devices with horizontal heating coil configurations as well as one with a sub-ohm resistance vertical heating coil. In order to understand and begin to address the origin of DHA and related aerosol products, the wicking properties of the three e-cigarettes were compared. DHA levels were analyzed by a combination of GS/MS and 1H NMR. DHA was found in all three e-cigarettes, with substantially less in the sub-ohm, vertical coil device as compared to the horizontal coil devices (e.g., 0.088 μg/puff vs. 2.29 μg/puff, respectively). Correspondingly, the temperature of the wet layer of the wick for the vertical coil was relatively stable, compared to the wicks for the horizontal coils, upon increasing battery power output. This result is in agreement with prior studies of e-cigarette wicking efficiency and aerosol toxin formation. The temperature measurements reported are a simple means for comparing devices with different design properties during operation.
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