Remediation of Thirdhand Tobacco Smoke with Ozone: Probing Deep Reservoirs in Carpets.

We assessed the efficacy of ozonation as an indoor remediation strategy by evaluating how a carpet serves as a sink and long-term source of thirdhand tobacco smoke (THS) while protecting contaminants absorbed in deep reservoirs by scavenging ozone. Specimens from unused carpet that was exposed to smoke in the lab ("fresh THS") and contaminated carpets retrieved from smokers' homes ("aged THS") were treated with 1000 ppb ozone in bench-scale tests. Nicotine was partially removed from fresh THS specimens by volatilization and oxidation, but it was not significantly eliminated from aged THS samples. By contrast, most of the 24 polycyclic aromatic hydrocarbons detected in both samples were partially removed by ozone. One of the home-aged carpets was installed in an 18 m3 room-sized chamber, where its nicotine emission rate was 950 ng day-1 m-2. In a typical home, such daily emissions could amount to a non-negligible fraction of the nicotine released by smoking one cigarette. The operation of a commercial ozone generator for a total duration of 156 min, reaching concentrations up to 10,000 ppb, did not significantly reduce the carpet nicotine loading (26-122 mg m-2). Ozone reacted primarily with carpet fibers, rather than with THS, leading to short-term emissions of aldehydes and aerosol particles. Hence, by being absorbed deeply into carpet fibers, THS constituents can be partially shielded from ozonation.

Thirdhand Exposures to Tobacco-Specific Nitrosamines through Inhalation, Dust Ingestion, Dermal Uptake, and Epidermal Chemistry.

Tobacco-specific nitrosamines (TSNAs) are emitted during smoking and form indoors by nitrosation of nicotine. Two of them, N'-nitrosonornicotine (NNN) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), are human carcinogens with No Significant Risk Levels (NSRLs) of 500 and 14 ng day-1, respectively. Another TSNA, 4-(methylnitrosamino)-4-(3-pyridyl) butanal (NNA), shows genotoxic and mutagenic activity in vitro. Here, we present additional evidence of genotoxicity of NNA, an assessment of TSNA dermal uptake, and predicted exposure risks through different pathways. Dermal uptake was investigated by evaluating the penetration of NNK and nicotine through mice skin. Comparable mouse urine metabolite profiles suggested that both compounds were absorbed and metabolized via similar mechanisms. We then investigated the effects of skin constituents on the reaction of adsorbed nicotine with nitrous acid (epidermal chemistry). Higher TSNA concentrations were formed on cellulose and cotton substrates that were precoated with human skin oils and sweat compared to clean substrates. These results were combined with reported air, dust, and surface concentrations to assess NNK intake. Five different exposure pathways exceeded the NSRL under realistic scenarios, including inhalation, dust ingestion, direct dermal contact, gas-to-skin deposition, and epidermal nitrosation of nicotine. These results illustrate potential long-term health risks for nonsmokers in homes contaminated with thirdhand tobacco smoke.

Volatile aldehyde emissions from "sub-ohm" vaping devices.

"Sub-ohm" atomizers with reduced resistance can deliver more power than conventional electronic cigarettes. Typical battery outputs are 100 W or more. These devices are particularly popular among young users, and can be a significant source of volatile carbonyls in the indoor environment. Emissions from next-generation sub-ohm vaping products were characterized by determining e-liquid consumption and volatile aldehydes emissions for several combinations of popular high-power configurations. Tests explored the effect of dilution air flow (air vent opening), puffing volume, and coil assembly configuration. The mass of liquid consumed per puff increased as the puff volume increased from 50 to 100 mL, then remained relatively constant for larger puff volumes up to 500 mL. This is likely due to mass transfer limitations at the wick and coil assembly, which reduced the vaporization rate at higher puff volumes. Carbonyl emission rates were systematically evaluated using a 0.15 Ω dual coil atomizer as a function of the puffing volume and dilution air flow, adjusted by setting the air vents to either 100% (fully open), 50%, 25%, or 0% (closed). The highest formaldehyde emissions were observed for the lowest puff volume (50 mL) when the vents were closed (48 ng mg-1), opened at 25% (39 ng mg-1) and at 50% (32 ng mg-1). By contrast, 50-mL puffs with 100% open vents, and puff volumes >100 mL for any vent aperture, generated formaldehyde yields of 20 ng mg-1 or lower, suggesting that a significant cooling effect resulted in limited carbonyl formation. Considering the effect of the coil resistance when operated at a voltage of 3.8 V, the amount of liquid evaporated per puff decreased as the resistance increased, in the order of 0.15 Ω > 0.25 Ω > 0.6 Ω, consistent with decreasing aerosol temperatures measured at the mouthpiece. Three different configurations of 0.15 Ω coils (dual, quadruple and octuple) were evaluated, observing significant variability. No clear trend was found between carbonyl emission rates and coil resistance or configuration, with highest emissions corresponding to a 0.25 Ω dual coil atomizer. Carbonyl emission rates were compared with those determined using the same methodology for conventional e-cigarettes (lower power tank systems), observing overall lower yields for the sub-ohm devices.

Emissions from Heated Terpenoids Present in Vaporizable Cannabis Concentrates.

Vaporizable cannabis concentrates (VCCs) consumed as a liquid (vaping) or a waxy solid (dabbing) are becoming increasingly popular. However, their associated emissions and impacts have not been fully described. Mixtures containing different proportions of 12 VCC terpenoids and high MW compounds were heated at 100-500 °C inside a room-sized chamber to simulate emissions. Terpenoids, thermal degradation byproducts, and ultrafine particles (UFPs) were quantified in the chamber air. Air samples contained over 50% of emitted monoterpenes and less than 40% of released sesquiterpenes and terpene alcohols. Eleven degradation byproducts were quantified, including acrolein (1.3-3.9 µg m-3) and methacrolein (2.0 µg m-3). A large amount of UFPs were released upon heating and remained airborne for at least 3 h. The mode diameter increased from 80 nm at 100 °C to 140 nm at 500 °C, and particles smaller than 250 nm contributed to 90% of PM1.0. The presence of 0.5% of lignin, flavonoid, and triterpene additives in the heated mixtures resulted in a threefold increase in the particle formation rate and PM1.0 concentration, suggesting that these high-molecular-weight compounds enhanced aerosol inception and growth. Predicted UFP emission rates in typical consumption scenarios (6 × 1011-2 × 1013 # min-1) were higher than, or comparable with, other common indoor sources such as smoking and cooking.

Chemical changes in thirdhand smoke associated with remediation using an ozone generator.

Ozonation is a common remediation approach to eliminate odors from mold, tobacco and fire damage in buildings. Little information exists to: 1) assess its effectiveness; 2) provide guidance on operation conditions; and 3) identify potential risks associated with the presence of indoor ozone and ozonation byproducts. The goal of this study is to evaluate chemical changes in thirdhand smoke (THS) aerosols induced by high levels of ozone, in comparison with THS aerosols aged under similar conditions in the absence of ozone. Samples representing different stages of smoke aging in the absence of ozone, including freshly emitted secondhand smoke (SHS) and THS, were collected inside an 18-m3 room-sized chamber over a period of 42 h after six cigarettes were consumed. The experiments involved collection and analysis of gas phase species including volatile organic compounds (VOCs), volatile carbonyls, semivolatile organic compounds (SVOCs), and particulate matter. VOC analysis was carried out by gas chromatography/mass spectrometry with a thermal desorption inlet (TD-GC/MS), and volatile carbonyls were analyzed by on-line derivatization with dinitrophenylhydrazine (DNPH), followed by liquid chromatography with UV/VIS detection. SVOCs were extracted from XAD-coated denuders and Teflon-coated fiberglass filters in the absence of ozone. In those extracts, tobacco-specific nitrosamines (TSNAs) and other SVOCs were analyzed by gas chromatography with positive chemical ionization-triple quadrupole mass spectrometric detection (GC/PCI-QQQ-MS), and polycyclic aromatic hydrocarbons (PAHs) were quantified by gas chromatography with ion trap mass spectrometric detection (GC/IT-MS) in selected ion monitoring mode. Particulate matter concentration was determined gravimetrically. In a second experiment, a 300 mg h-1 commercial ozone generator was operated during 1 h, one day after smoke was generated, to evaluate the remediation of THS by ozonation. VOCs and volatile carbonyls were analyzed before and after ozonation. Extracts from fabrics that were exposed in the chamber before and after ozonation as surrogates for indoor furnishings were analyzed by GC/IT-MS, and aerosol size distribution was studied with a scanning mobility particle sizer. Ozone concentration was measured with a photometric detector. An estimated 175 mg ozone reacted with THS after 1 h of treatment, corresponding to 58% of the total O3 released during that period. Fabric-bound nicotine was depleted after ozonation, and the surface concentration of PAHs adsorbed to fabric specimens decreased by an order of magnitude due to reaction with ozone, reaching pre-smoking levels. These results suggest that ozonation has the potential to remove harmful THS chemicals from indoor surfaces. However, gas phase concentrations of volatile carbonyls, including formaldehyde, acetaldehyde and acetone were higher immediately after ozonation. Ultrafine particles (UFP, in most cases with size <60 nm) were a major ozonation byproduct. UFP number concentrations peaked shortly after ozonation ended, and remained at higher-than background levels for several hours. Based on these results, minimum re-entry times after ozone treatment were predicted for different indoor scenarios. Clearly defining re-entry times can serve as a practical measure to prevent acute exposures to ozone and harmful ozonation byproducts after treatment. This study evaluated potential benefits and risks associated with THS remediation using ozone, providing insights into this technology.

Air Pollutant Emission Rates for Dry Anaerobic Digestion and Composting of Organic Municipal Solid Waste.

Dry anaerobic digestion (AD) of organic municipal solid waste (MSW) followed by composting of the residual digestate is a waste diversion strategy that generates biogas and soil amendment products. The AD-composting process avoids methane (CH4) emissions from landfilling, but emissions of other greenhouse gases, odorous/toxic species, and reactive compounds can affect net climate and air quality impacts. In situ measurements of key sources at two large-scale industrial facilities in California were conducted to quantify pollutant emission rates across the AD-composting process. These measurements established a strong relationship between flared biogas ammonia (NH3) content and emitted nitrogen oxides (NOx), indicating that fuel NOx formation is significant and dominates over the thermal or prompt NOx pathways when biogas NH3 concentration exceeds ∼200 ppm. Composting is the largest source of CH4, carbon dioxide (CO2), nitrous oxide (N2O), and carbon monoxide (CO) emissions (∼60-70%), and dominate NH3, hydrogen sulfide (H2S), and volatile organic compounds (VOC) emissions (>90%). The high CH4 contribution to CO2-equivalent emissions demonstrates that composting can be an important CH4 source, which could be reduced with improved aeration. Controlling greenhouse gas and toxic/odorous emissions from composting offers the greatest mitigation opportunities for reducing the climate and air quality impacts of the AD-composting process.

Heated Tobacco Products: Volatile Emissions and Their Predicted Impact on Indoor Air Quality.

This study characterized emissions from IQOS, a heated tobacco product promoted as a less harmful alternative to cigarettes. Consumable tobacco plugs were analyzed by headspace GC/MS to assess the influence of heating temperature on the emission profile. Yields of major chemical constituents increased from 4.1 mg per unit at 180 °C to 6.2 mg at 200 °C, and 10.5 mg at 220 °C. The Health Canada Intense smoking regime was used to operate IQOS in an environmental chamber, quantifying 33 volatile organic compounds in mainstream and sidestream emissions. Aldehydes, nitrogenated species, and aromatic species were found, along with other harmful and potentially harmful compounds. Compared with combustion cigarettes, IQOS yields were in most cases 1-2 orders of magnitude lower. However, yields were closer to, and sometimes higher than electronic cigarettes. Predicted users' daily average intake of benzene, formaldehyde, acetaldehyde and acrolein were 39 µg, 32 µg, 2.2 mg and 71 µg, respectively. Indoor air concentrations were estimated for commonly encountered scenarios, with acrolein levels of concern (over 0.35 µg m-3) derived from IQOS used in homes and public spaces. Heated tobacco products are a weaker indoor pollution source than conventional cigarettes, but their impacts are neither negligible nor yet fully understood.

Emissions from Electronic Cigarettes: Assessing Vapers' Intake of Toxic Compounds, Secondhand Exposures, and the Associated Health Impacts.

E-cigarettes likely represent a lower risk to health than traditional combustion cigarettes, but they are not innocuous. Recently reported emission rates of potentially harmful compounds were used to assess intake and predict health impacts for vapers and bystanders exposed passively. Vapers' toxicant intake was calculated for scenarios in which different e-liquids were used with various vaporizers, battery power settings and vaping regimes. For a high rate of 250 puff day-1 using a typical vaping regime and popular tank devices with battery voltages from 3.8 to 4.8 V, users were predicted to inhale formaldehyde (up to 49 mg day-1), acrolein (up to 10 mg day-1) and diacetyl (up to 0.5 mg day-1), at levels that exceeded U.S. occupational limits. Formaldehyde intake from 100 daily puffs was higher than the amount inhaled by a smoker consuming 10 conventional cigarettes per day. Secondhand exposures were predicted for two typical indoor scenarios: a home and a bar. Contributions from vaping to air pollutant concentrations in the home did not exceed the California OEHHA 8-h reference exposure levels (RELs), except when a high emitting device was used at 4.8 V. In that extreme scenario, the contributions from vaping amounted to as much as 12 µg m-3 formaldehyde and 2.6 µg m-3 acrolein. Pollutant concentrations in bars were modeled using indoor volumes, air exchange rates and the number of hourly users reported in the literature for U.S. bars in which smoking was allowed. Predicted contributions to indoor air levels were higher than those in the residential scenario. Formaldehyde (on average 135 µg m-3) and acrolein (28 µg m-3) exceeded the acute 1-h exposure REL for the highest emitting vaporizer/voltage combination. Predictions for these compounds also exceeded the 8-h REL in several bars when less intense vaping conditions were considered. Benzene concentrations in a few bars approached the 8-h REL, and diacetyl levels were close to the lower limit for occupational exposures. The integrated health damage from passive vaping was derived by computing disability-adjusted life years (DALYs) lost due to exposure to secondhand vapor. Acrolein was the dominant contributor to the aggregate harm. DALYs for the various device/voltage combinations were lower than-or comparable to-those estimated for exposures to secondhand and thirdhand tobacco smoke.

Emissions from Electronic Cigarettes: Key Parameters Affecting the Release of Harmful Chemicals.

Use of electronic cigarettes has grown exponentially over the past few years, raising concerns about harmful emissions. This study quantified potentially toxic compounds in the vapor and identified key parameters affecting emissions. Six principal constituents in three different refill "e-liquids" were propylene glycol (PG), glycerin, nicotine, ethanol, acetol, and propylene oxide. The latter, with mass concentrations of 0.4-0.6%, is a possible carcinogen and respiratory irritant. Aerosols generated with vaporizers contained up to 31 compounds, including nicotine, nicotyrine, formaldehyde, acetaldehyde, glycidol, acrolein, acetol, and diacetyl. Glycidol is a probable carcinogen not previously identified in the vapor, and acrolein is a powerful irritant. Emission rates ranged from tens to thousands of nanograms of toxicants per milligram of e-liquid vaporized, and they were significantly higher for a single-coil vs a double-coil vaporizer (by up to an order of magnitude for aldehydes). By increasing the voltage applied to a single-coil device from 3.3 to 4.8 V, the mass of e-liquid consumed doubled from 3.7 to 7.5 mg puff(-1) and the total aldehyde emission rates tripled from 53 to 165 µg puff(-1), with acrolein rates growing by a factor of 10. Aldehyde emissions increased by more than 60% after the device was reused several times, likely due to the buildup of polymerization byproducts that degraded upon heating. These findings suggest that thermal degradation byproducts are formed during vapor generation. Glycidol and acrolein were primarily produced by glycerin degradation. Acetol and 2-propen-1-ol were produced mostly from PG, while other compounds (e.g., formaldehyde) originated from both. Because emissions originate from reaction of the most common e-liquid constituents (solvents), harmful emissions are expected to be ubiquitous when e-cigarette vapor is present.

Effect of temperature and humidity on formaldehyde emissions in temporary housing units.

The effect of temperature and humidity on formaldehyde emissions from samples collected from temporary housing units (THUs) was studied. The THUs were supplied by the U.S. Federal Emergency Management Administration (FEMA) to families that lost their homes in Louisiana and Mississippi during the Hurricane Katrina and Rita disasters. On the basis of a previous study, four of the composite wood surface materials that dominated contributions to indoor formaldehyde were selected to analyze the effects of temperature and humidity on the emission factors. Humidity equilibration experiments were carried out on two of the samples to determine how long the samples take to equilibrate with the surrounding environmental conditions. Small chamber experiments were then conducted to measure emission factors for the four surface materials at various temperature and humidity conditions. The samples were analyzed for formaldehyde via high-performance liquid chromatography. The experiments showed that increases in temperature or humidity contributed to an increase in emission factors. A linear regression model was built using the natural log of the percent relative humidity (RH) and inverse of temperature (in K) as independent variables and the natural log of emission factors as the dependent variable. The coefficients for the inverse of temperature and log RH with log emission factor were found to be statistically significant for all of the samples at the 95% confidence level. This study should assist in retrospectively estimating indoor formaldehyde exposure of occupants of THUs.