Monitoring redox stress in human airway epithelial cells exposed to woodsmoke at an air-liquid interface.

Wildland fires contribute significantly to the ambient air pollution burden worldwide, causing a range of adverse health effects in exposed populations. The toxicity of woodsmoke, a complex mixture of gases, volatile organic compounds, and particulate matter, is commonly studied in vitro using isolated exposures of conventionally cultured lung cells to either resuspended particulate matter or organic solvent extracts of smoke, leading to incomplete toxicity evaluations. This study aimed to improve our understanding of the effects of woodsmoke inhalation by building an advanced in vitro exposure system that emulates human exposure of the airway epithelium. We report the development and characterization of an innovative system that permits live-cell monitoring of the intracellular redox status of differentiated primary human bronchial epithelial cells cultured at an air-liquid interface (pHBEC-ALI) as they are exposed to unfractionated woodsmoke generated in a tube furnace in real time. pHBEC-ALI exposed to freshly generated woodsmoke showed oxidative changes that were dose-dependent and reversible, and not attributable to carbon monoxide exposure. These findings show the utility of this novel system for studying the molecular initiating events underlying woodsmoke-induced toxicity in a physiologically relevant in vitro model, and its potential to provide biological plausibility for risk assessment and public health measures.

Cookstove Emissions and Performance Evaluation Using a New ISO Protocol and Comparison of Results with Previous Test Protocols.

In 2018, the International Organization for Standardization (ISO) 19867-1 "Harmonized laboratory test protocols" were released for establishing improved quality and comparability for data on cookstove air pollutant emissions, efficiency, safety, and durability. This is the first study that compares emissions [carbon dioxide, carbon monoxide, total hydrocarbons, methane, nitrogen oxides, fine particulate matter (PM2.5), organic carbon, elemental carbon, and ultrafine particles] and efficiency data between the ISO protocol and the Water Boiling Test (WBT). The study examines six stove/fuel combinations [liquefied petroleum gas (LPG), pellet, wood fan, wood rocket, three stone fire, and charcoal] tested in the same US EPA laboratory. Evaluation of the ISO protocol shows improvements over previous test protocols and that results are relatively consistent with former WBT data in terms of tier ratings for emissions and efficiency, as defined by the ISO 19867-3 "Voluntary Performance Targets." Most stove types remain similarly ranked using ISO and WBT protocols, except charcoal and LPG are in higher PM2.5 tiers with the ISO protocol. Additionally, emissions data including polycyclic aromatic hydrocarbons are utilized to compare between the ISO and Firepower Sweep Test (FST) protocols. Compared to the FST, the ISO protocol results in generally higher PM2.5 tier ratings.

Censoring Trace-Level Environmental Data: Statistical Analysis Considerations to Limit Bias.

Trace-level environmental data typically include values near or below detection and quantitation thresholds where health effects may result from low-concentration exposures to one chemical over time or to multiple chemicals. In a cook stove case study, bias in dibenzo[a,h]anthracene concentration means and standard deviations (SDs) was assessed following censoring at thresholds for selected analysis approaches: substituting threshold/2, maximum likelihood estimation, robust regression on order statistics, Kaplan-Meier, and omitting censored observations. Means and SDs for gas chromatography-mass spectrometry-determined concentrations were calculated after censoring at detection and calibration thresholds, 17% and 55% of the data, respectively. Threshold/2 substitution was the least biased. Measurement values were subsequently simulated from two log-normal distributions at two sample sizes. Means and SDs were calculated for 30%, 50%, and 80% censoring levels and compared to known distribution counterparts. Simulation results illustrated (1) threshold/2 substitution to be inferior to modern after-censoring statistical approaches and (2) all after-censoring approaches to be inferior to including all measurement data in analysis. Additionally, differences in stove-specific group means were tested for uncensored samples and after censoring. Group differences of means tests varied depending on censoring and distributional decisions. Investigators should guard against censoring-related bias from (explicit or implicit) distributional and analysis approach decisions.

Chemistry, lung toxicity and mutagenicity of burn pit smoke-related particulate matter.

BACKGROUND: Open burning of anthropogenic sources can release hazardous emissions and has been associated with increased prevalence of cardiopulmonary health outcomes. Exposure to smoke emitted from burn pits in military bases has been linked with respiratory illness among military and civilian personnel returning from war zones. Although the composition of the materials being burned is well studied, the resulting chemistry and potential toxicity of the emissions are not. METHODS: Smoke emission condensates from either flaming or smoldering combustion of five different types of burn pit-related waste: cardboard; plywood; plastic; mixture; and mixture/diesel, were obtained from a laboratory-scale furnace coupled to a multistage cryotrap system. The primary emissions and smoke condensates were analyzed for a standardized suite of chemical species, and the condensates were studied for pulmonary toxicity in female CD-1 mice and mutagenic activity in Salmonella (Ames) mutagenicity assay using the frameshift strain TA98 and the base-substitution strain TA100 with and without metabolic activation (S9 from rat liver). RESULTS: Most of the particles in the smoke emitted from flaming and smoldering combustion were less than 2.5 µm in diameter. Burning of plastic containing wastes (plastic, mixture, or mixture/diesel) emitted larger amounts of particulate matter (PM) compared to other types of waste. On an equal mass basis, the smoke PM from flaming combustion of plastic containing wastes caused more inflammation and lung injury and was more mutagenic than other samples, and the biological responses were associated with elevated polycyclic aromatic hydrocarbon levels. CONCLUSIONS: This study suggests that adverse health effects of burn pit smoke exposure vary depending on waste type and combustion temperature; however, burning plastic at high temperature was the most significant contributor to the toxicity outcomes. These findings will provide a better understanding of the complex chemical and combustion temperature factors that determine toxicity of burn pit smoke and its potential health risks at military bases.

The role of fuel type and combustion phase on the toxicity of biomass smoke following inhalation exposure in mice.

The characteristics of wildland fire smoke exposures which initiate or exacerbate cardiopulmonary conditions are unclear. We previously reported that, on a mass basis, lung toxicity associated with particulate matter (PM) from flaming smoke aspirated into mouse lungs is greater than smoldering PM. In this study, we developed a computer-controlled inhalation system which can precisely control complex biomass smoke emissions from different combustion conditions. This system was used to examine the toxicity of inhaled biomass smoke from peat, eucalyptus, and oak fuels generated under smoldering and flaming phases with emissions set to the same approximate concentration of carbon monoxide (CO) for each exposure (60-110 ppm), resulting in PM levels of ~ 4 mg/m3 for flaming and ~ 40 mg/m3 for smoldering conditions. Mice were exposed by inhalation 1 h/day for 2 days, and assessed for lung toxicity at 4 and 24 h after the final exposure. Peat (flaming and smoldering) and eucalyptus (smoldering) smoke elicited significant inflammation (neutrophil influx) in mouse lungs at 4 h with the peat (flaming) smoke causing even greater lung inflammation at 24-h post-exposure. A significant alteration in ventilatory timing was also observed in mice exposed to the peat (flaming) and eucalyptus (flaming and smoldering) smoke immediately after each day of exposure. No responses were seen for exposures to similar concentrations of flaming or smoldering oak smoke. The lung toxicity potencies (neutrophil influx per PM mass) agreed well between the inhalation and previously reported aspiration studies, demonstrating that although flaming smoke contains much less PM mass than smoldering smoke, it is more toxic on a mass basis than smoldering smoke exposure, and that fuel type is also a controlling factor.

An assessment of important SPECIATE profiles in the EPA emissions modeling platform and current data gaps.

The United States (US) Environmental Protection Agency (EPA)'s SPECIATE database contains speciated particulate matter (PM) and volatile organic compound (VOC) emissions profiles. Emissions profiles from anthropogenic combustion, industry, wildfires, and agricultural sources among others are key inputs for creating chemically-resolved emissions inventories for air quality modeling. While the database and its use for air quality modeling are routinely updated and evaluated, this work sets out to systematically prioritize future improvements and communicate speciation data needs to the research community. We first identify the most prominent profiles (PM and VOC) used in the EPA's 2014 emissions modeling platform based on PM mass and VOC mass and reactivity. It is important to note that the on-road profiles were excluded from this analysis since speciation for these profiles is computed internally in the MOVES model. We then investigate these profiles further for quality and to determine whether they were being appropriately matched to source types while also considering regional variability of speciated pollutants. We then applied a quantitative needs assessment ranking system which rates the profile based on age, appropriateness (i.e. is the profile being used appropriately), prevalence in the EPA modeling platform and the quality of the reference. Our analysis shows that the highest ranked profiles (e.g. profile assignments with the highest priority for updates) include PM2.5 profiles for fires (prescribed, agricultural and wild) and VOC profiles for crude oil storage tanks and residential wood combustion of pine wood. Top ranked profiles may indicate either that there are problems with the currently available source testing or that current mappings of profiles to source categories within EPA's modeling platform need improvement. Through this process, we have identified 29 emissions sourcecategories that would benefit from updated mapping. Many of these mapping mismatches are due to lack of emissions testing for appropriate source categories. In addition, we conclude that new source emissions testing would be especially beneficial for residential wood combustion, nonroad gasoline exhaust and nonroad diesel equipment.

Evaluating the Performance of Household Liquefied Petroleum Gas Cookstoves.

Liquefied petroleum gas (LPG) cookstoves are considered to be an important solution for mitigating household air pollution; however, their performance has rarely been evaluated. To fill the data and knowledge gaps in this important area, 89 laboratory tests were conducted to quantify efficiencies and pollutant emissions from five commercially available household LPG stoves under different burning conditions. The mean thermal efficiency (±standard deviation) for the tested LPG cookstoves was 51 ± 6%, meeting guidelines for the highest tier level (Tier 4) under the International Organization for Standardization, International Workshop Agreement 11. Emission factors of CO2, CO, THC, CH4, and NOx on the basis of useful energy delivered (MJd) were 142 ± 17, 0.77 ± 0.55, 130 ± 196, 5.6 ± 8.2, and 46 ± 9 mg/MJd, respectively. Approximately 90% of the PM2.5 data were below the detection limit, corresponding to an emission rate below 0.11 mg/min. For those data above the detection limit, the average emission factor was 2.4 ± 1.6 mg/MJd, with a mean emission rate of 0.20 ± 0.16 mg/min. Under the specified gas pressure (2.8 kPa), but with the burner control set to minimum air flow rate, less complete combustion resulted in a visually yellow flame, and CO, PM2.5, EC, and BC emissions all increased. LPG cookstoves met guidelines for Tier 4 for both CO and PM2.5 emissions and mostly met the World Health Organization Emission Rate Targets set to protect human health.

Light Absorption of Secondary Organic Aerosol: Composition and Contribution of Nitroaromatic Compounds.

Secondary organic aerosol (SOA) can affect the atmospheric radiation balance through absorbing light at shorter visible and UV wavelengths. However, the composition and optical properties of light-absorbing SOA is poorly understood. In this work, SOA filter samples were collected during individual chamber experiments conducted with three biogenic and eight aromatic volatile organic compound (VOC) precursors in the presence of NOX and H2O2. Compared with the SOA generated using the aromatic precursors, biogenic SOA generally exhibits negligible light absorption above 350 nm; the aromatic SOA generated in the presence of NOX shows stronger light absorption than that generated with H2O2. Fifteen nitroaromatic compound (NAC) chemical formulas were identified and quantified in SOA samples. Their contributions to the light absorption of sample extracts were also estimated. On average, the m-cresol/NOX SOA sample has the highest mass contribution from NACs (10.4 ± 6.74%, w/w), followed by naphthalene/NOX (6.41 ± 2.08%) and benzene/NOX (5.81 ± 3.82%) SOA. The average contributions of NACs to total light absorption were at least two times greater than their average mass contributions at 365 and 400 nm, revealing the potential use of chromophoric NACs as brown carbon (BrC) tracers in source apportionment and air quality modeling studies.

A Laboratory Comparison of Emission Factors, Number Size Distributions, and Morphology of Ultrafine Particles from 11 Different Household Cookstove-Fuel Systems.

Ultrafine particle (UFP) emissions and particle number size distributions (PNSD) are critical in the evaluation of air pollution impacts; however, data on UFP number emissions from cookstoves, which are a major source of many pollutants, are limited. In this study, 11 fuel-stove combinations covering a variety of fuels and different stoves are investigated for UFP emissions and PNSD. The combustion of LPG and alcohol (∼1011 particles per useful energy delivered, particles/MJd), and kerosene (∼1013 particles/MJd), produced emissions that were lower by 2-3 orders of magnitude than solid fuels (1014-1015 particles/MJd). Three different PNSD types-unimodal distributions with peaks ∼30-40 nm, unimodal distributions with peaks <30 nm, and bimodal distributions-were observed as the result of both fuel and stove effects. The fractions of particles smaller than 30 nm (F30) varied among the tested systems, ranging from 13% to 88%. The burning of LPG and alcohol had the lowest PM2.5 mass emissions, UFP number emissions, and F30 (13-21% for LPG and 35-41% for alcohol). Emissions of PM2.5 and UFP from kerosene were also low compared with solid fuel burning but had a relatively high F30 value of approximately 73-80%.

Effects of Cold Temperature and Ethanol Content on VOC Emissions from Light-Duty Gasoline Vehicles.

Emissions of speciated volatile organic compounds (VOCs), including mobile source air toxics (MSATs), were measured in vehicle exhaust from three light-duty spark ignition vehicles operating on summer and winter grade gasoline (E0) and ethanol blended (E10 and E85) fuels. Vehicle testing was conducted using a three-phase LA92 driving cycle in a temperature-controlled chassis dynamometer at two ambient temperatures (-7 and 24 °C). The cold start driving phase and cold ambient temperature increased VOC and MSAT emissions up to several orders of magnitude compared to emissions during other vehicle operation phases and warm ambient temperature testing, respectively. As a result, calculated ozone formation potentials (OFPs) were 7 to 21 times greater for the cold starts during cold temperature tests than comparable warm temperature tests. The use of E85 fuel generally led to substantial reductions in hydrocarbons and increases in oxygenates such as ethanol and acetaldehyde compared to E0 and E10 fuels. However, at the same ambient temperature, the VOC emissions from the E0 and E10 fuels and OFPs from all fuels were not significantly different. Cold temperature effects on cold start MSAT emissions varied by individual MSAT compound, but were consistent over a range of modern spark ignition vehicles.

Cold temperature and biodiesel fuel effects on speciated emissions of volatile organic compounds from diesel trucks.

Speciated volatile organic compounds (VOCs) were measured in diesel exhaust from three heavy-duty trucks equipped with modern aftertreatment technologies. Emissions testing was conducted on a chassis dynamometer at two ambient temperatures (-7 and 22 °C) operating on two fuels (ultra low sulfur diesel and 20% soy biodiesel blend) over three driving cycles: cold start, warm start and heavy-duty urban dynamometer driving cycle. VOCs were measured separately for each drive cycle. Carbonyls such as formaldehyde and acetaldehyde dominated VOC emissions, making up ∼ 72% of the sum of the speciated VOC emissions (∑VOCs) overall. Biodiesel use led to minor reductions in aromatics and variable changes in carbonyls. Cold temperature and cold start conditions caused dramatic enhancements in VOC emissions, mostly carbonyls, compared to the warmer temperature and other drive cycles, respectively. Different 2007+ aftertreatment technologies involving catalyst regeneration led to significant modifications of VOC emissions that were compound-specific and highly dependent on test conditions. A comparison of this work with emission rates from different diesel engines under various test conditions showed that these newer technologies resulted in lower emission rates of aromatic compounds. However, emissions of other toxic partial combustion products such as carbonyls were not reduced in the modern diesel vehicles tested.

Quantifying functional group compositions of household fuel-burning emissions.

Globally, billions of people burn fuels indoors for cooking and heating, which contributes to millions of chronic illnesses and premature deaths annually. Additionally, residential burning contributes significantly to black carbon emissions, which have the highest global warming impacts after carbon dioxide and methane. In this study, we use Fourier transform infrared spectroscopy (FTIR) to analyze fine-particulate emissions collected on Teflon membrane filters from 15 cookstove types and 5 fuel types. Emissions from three fuel types (charcoal, kerosene, and red oak wood) were found to have enough FTIR spectral response for functional group (FG) analysis. We present distinct spectral profiles for particulate emissions of these three fuel types. We highlight the influential FGs constituting organic carbon (OC) using a multivariate statistical method and show that OC estimates by collocated FTIR and thermal-optical transmittance (TOT) are highly correlated, with a coefficient determination of 82.5 %. As FTIR analysis is fast and non-destructive and provides complementary FG information, the analysis method demonstrated herein can substantially reduce the need for thermal-optical measurements for source emissions.

Burn pit-related smoke causes developmental and behavioral toxicity in zebrafish: Influence of material type and emissions chemistry.

Combustion of mixed materials during open air burning of refuse or structural fires in the wildland urban interface produces emissions that worsen air quality, contaminate rivers and streams, and cause poor health outcomes including developmental effects. The zebrafish, a freshwater fish, is a useful model for quickly screening the toxicological and developmental effects of agents in such species and elicits biological responses that are often analogous and predictive of responses in mammals. The purpose of this study was to compare the developmental toxicity of smoke derived from the burning of 5 different burn pit-related material types (plywood, cardboard, plastic, a mixture of the three, and the mixture plus diesel fuel as an accelerant) in zebrafish larvae. Larvae were exposed to organic extracts of increasing concentrations of each smoke 6-to-8-hr post fertilization and assessed for morphological and behavioral toxicity at 5 days post fertilization. To examine chemical and biological determinants of toxicity, responses were related to emissions concentrations of polycyclic hydrocarbons (PAH). Emissions from plastic and the mixture containing plastic caused the most pronounced developmental effects, including mortality, impaired swim bladder inflation, pericardial edema, spinal curvature, tail kinks, and/or craniofacial deformities, although all extracts caused concentration-dependent effects. Plywood, by contrast, altered locomotor responsiveness to light changes to the greatest extent. Some morphological and behavioral responses correlated strongly with smoke extract levels of PAHs including 9-fluorenone. Overall, the findings suggest that material type and emissions chemistry impact the severity of zebrafish developmental toxicity responses to burn pit-related smoke.

Carbonaceous aerosols emitted from light-duty vehicles operating on gasoline and ethanol fuel blends.

This study examines the chemical properties of carbonaceous aerosols emitted from three light-duty gasoline vehicles (LDVs) operating on gasoline (e0) and ethanol-gasoline fuel blends (e10 and e85). Vehicle road load simulations were performed on a chassis dynamometer using the three-phase LA-92 unified driving cycle (UDC). Effects of LDV operating conditions and ambient temperature (-7 and 24 °C) on particle-phase semivolatile organic compounds (SVOCs) and organic and elemental carbon (OC and EC) emissions were investigated. SVOC concentrations and OC and EC fractions were determined with thermal extraction-gas chromatography-mass spectrometry (TE-GC-MS) and thermal-optical analysis (TOA), respectively. LDV aerosol emissions were predominantly carbonaceous, and EC/PM (w/w) decreased linearly with increasing fuel ethanol content. TE-GC-MS analysis accounted for up to 4% of the fine particle (PM2.5) mass, showing the UDC phase-integrated sum of identified SVOC emissions ranging from 0.703 µg km(-1) to 18.8 µg km(-1). Generally, higher SVOC emissions were associated with low temperature (-7 °C) and engine ignition; mixed regression models suggest these emissions rate differences are significant. Use of e85 significantly reduced the emissions of lower molecular weight PAH. However, a reduction in higher molecular weight PAH entities in PM was not observed. Individual SVOC emissions from the Tier 2 LDVs and fuel technologies tested are substantially lower and distributed differently than those values populating the United States emissions inventories currently. Hence, this study is likely to influence future apportionment, climate, and air quality model predictions that rely on source combustion measurements of SVOCs in PM.

Pollutant emissions and energy efficiency under controlled conditions for household biomass cookstoves and implications for metrics useful in setting international test standards.

Realistic metrics and methods for testing household biomass cookstoves are required to develop standards needed by international policy makers, donors, and investors. Application of consistent test practices allows emissions and energy efficiency performance to be benchmarked and enables meaningful comparisons among traditional and advanced stove types. In this study, 22 cookstoves burning six fuel types (wood, charcoal, pellets, corn cobs, rice hulls, and plant oil) at two fuel moisture levels were examined under laboratory-controlled operating conditions as outlined in the Water Boiling Test (WBT) protocol, Version 4. Pollutant emissions (carbon dioxide, carbon monoxide, methane, total hydrocarbons, and ultrafine particles) were continuously monitored. Fine particle mass was measured gravimetrically for each WBT phase. Additional measurements included cookstove power, energy efficiency, and fuel use. Emission factors are given on the basis of fuel energy, cooking energy, fuel mass, time, and cooking task or activity. The lowest PM(2.5) emissions were 74 mg MJ(delivered)(-1) from a technologically advanced cookstove compared with 700-1400 mg MJ(delivered)(-1) from the base-case open 3-stone cookfire. The highest thermal efficiency was 53% compared with 14-15% for the 3-stone cookfire. Based on these laboratory-controlled test results and observations, recommendations for developing potentially useful metrics for setting international standards are suggested.

XPS analysis of combustion aerosols for chemical composition, surface chemistry, and carbon chemical state.

Carbonaceous aerosols can vary in elemental content, surface chemistry, and carbon nano-structure. Each of these properties is related to the details of soot formation. Fuel source, combustion process (affecting formation and growth conditions), and postcombustion exhaust where oxidation occurs all contribute to the physical structure and surface chemistry of soot. Traditionally such physical and chemical parameters have been measured separately by various techniques. Presented here is the unified measurement of these characteristics using X-ray photoelectron spectroscopy (XPS). In the present study, XPS is applied to combustion soot collected from a diesel engine (running biodiesel and pump-grade fuels); jet engine; and institutional, plant, and residential oil-fired boilers. Elemental composition is mapped by a survey scan over a broad energy range. Surface chemistry and carbon nanostructure are quantified by deconvolution of high-resolution scans over the C1s region. This combination of parameters forms a distinct matrix of identifiers for the soots from these sources.

An advanced LC-MS (Q-TOF) technique for the detection of amino acids in atmospheric aerosols.

Methodology for detection of native (underivatized) amino acids (AA) in atmospheric aerosols has been developed. This article describes the use of LC-MS (Q-TOF) and microwave-assisted gas phase hydrolysis for detection of free and combined amino acids in aerosols collected in a Southeastern U.S. forest environment. Accurate mass detection and the addition of isotopically labeled surrogates prior to sample preparation allows for sensitive quantitation of target AA in a complex aerosol matrix. A total of 16 native AA were detected above the reporting threshold as water-soluble free AA, with an average concentration of 22 ± 9 ng m(-3) (N = 13). Following microwave-assisted gas phase hydrolysis, the total AA concentration in the forest environment increased significantly (70 ± 35 ng m(-3)) and additional compounds (methionine, isoleucine) were detected above the reporting threshold. The ability to quantify AA in aerosol samples without derivatization reduces time-consuming preparation procedures while providing the advancement of selective mass determination for important organic nitrogen (ON) species. Details on sample preparation that eliminates the freeze-drying approach typically practiced for water removal with biological samples, and vapor phase microwave hydrolysis parameters are provided. Method application for determination of atmospheric ON is discussed.

Quantitative assessment of elemental carbon in the lungs of never smokers, cigarette smokers, and coal miners.

Inhalation exposure to particulates such as cigarette smoke and coal dust is known to contribute to the development of chronic lung disease. The purpose of this study was to estimate the amount of elemental carbon (EC) deposits from autopsied lung samples from cigarette smokers, miners, and control subjects and explore the relationship between EC level, exposure history, and the extent of chronic lung disease. The samples comprised three subgroups representing never smokers (8), chronic cigarette smokers (26), and coal miners (6). Following the dissolution of lung tissue, the extracted EC residue was quantified using a thermal-optical transmission (TOT) carbon analyzer. Mean EC levels in the lungs of the control group were 56.68 ± 24.86 (SD) µg/g dry lung weight. Respective mean EC values in lung samples from the smokers and coal miners were 449.56 ± 320.3 µg/g and 6678.2 ± 6162 µg/g. These values were significantly higher than those obtained from the never-smoker group. EC levels in the lung and pack-years of cigarette smoking correlated significantly, as did EC levels and the severity of small airway disease. This study provides one of the first quantitative assessments of EC in human lungs from populations at high relative risk for the development of chronic lung disease.