Fresh and atmospherically aged biomass-burning (BB) aerosol mass is mostly comprised of strongly light-absorbing black carbon (BC) and of organic carbon (OC) with its light-absorbing fraction – brown carbon (BrC). There is a lack of data on the physical and chemical properties of atmospheric BB aerosols, leading to high uncertainties in estimates of the BB impact on air quality and climate, especially for BrC. The polarity of chemical compounds influences their fate in the atmosphere including wet/dry deposition and chemical and physical processing. So far, most of the attention has been given to the water-soluble (polar) fraction of BrC, while the non-polar BrC fraction has been largely ignored. In the present study, the light absorption properties of polar and non-polar fractions of fresh and aged BB emissions were examined to estimate the contribution of different-polarity organic compounds to the light absorption properties of BB aerosols. In our experiments, four globally and regionally important fuels were burned under flaming and smoldering conditions in the Desert Research Institute (DRI) combustion chamber. To mimic atmospheric oxidation processes (5–7 days), BB emissions were aged using an oxidation flow reactor (OFR). Fresh and OFR-aged BB aerosols were collected on filters and extracted with water and hexane to study absorption properties of polar and non-polar organic species. Results of spectrophotometric measurements (absorption weighted by the solar spectrum and normalized to mass of fuel consumed) over the 190 to 900 nm wavelength range showed that the non-polar (hexane-soluble) fraction is 2–3 times more absorbing than the polar (water-soluble) fraction. However, for emissions from fuels that undergo flaming combustion, an increased absorbance was observed for the water extracts of oxidized/aged emissions while the absorption of the hexane extracts was lower for the aged emissions for the same type of fuels. Absorption Ångström exponent (AAE) values, computed based on absorbance values from spectrophotometer measurements, were changed with aging and the nature of this change was fuel dependent. The light absorption by humic-like substances (HULIS) was found to be higher in fuels characteristic of the southwestern USA. The absorption of the HULIS fraction was lower for OFR-aged BB emissions. Comparison of the light absorption properties of different-polarity extracts (water, hexane, HULIS) provides insight into the chemical nature of BB BrC and its transformation during oxidation processes.
Dangerous levels of harmful chemicals in electronic cigarette (e-cigarette) aerosols were reported by several studies, but variability in e-cigarette design and use patterns, and a rapid development of new devices, such as JUUL, hamper efforts to develop standardized testing protocols and understand health risks associated with e-cigarette use. In this study, we investigated the relative importance of e-cigarette design, power output, liquid composition, puff topography on e-cigarette emissions of carbonyl compounds, carbon monoxide (CO), and nicotine. Four popular e-cigarette devices representing the most common e-cigarette types (e.g., cig-a-like, top-coil, ‘mod’, and ‘pod’) were tested. Under the tested vaping conditions, a top-coil device generated the highest amounts of formaldehyde and CO. A ‘pod’ type device (i.e., JUUL) emitted the highest amounts of nicotine, while generating the lowest levels of carbonyl and CO as compared to other tested e-cigarettes. Emissions increased nearly linearly with puff duration, while puff flow had a relatively small effect. Flavored e-liquids generated more carbonyls and CO than unflavored liquids. Carbonyl concentrations and CO in e-cigarette aerosols were found to be well correlated. While e-cigarettes emitted generally less CO and carbonyls than conventional cigarettes, daily carbonyl exposures from e-cigarette use could still exceed acute exposure limits, with the top-coil device potentially posing more harm than conventional cigarettes.
Several studies have shown the presence of aldehydes (i.e., formaldehyde, acrolein) in mainstream emissions of some e-cigarettes. For this reason, concerns have been raised regarding potential toxicity. The purpose of this research was to measure levels of carbonyls in exhaled breath of e-cigarette users during “vaping” sessions and estimate the respiratory tract (RT) uptake of specific aldehydes, including formaldehyde and acetaldehyde. We measured concentrations of 12 carbonyls in e-cigarette aerosols produced directly by e-cigarettes and in the exhaled breath of 12 participants (19 sessions). Carbonyls were sampled on 2,4-dinitrophenylhydrazine (DNPH) cartridges and analyzed with high performance liquid chromatography (HPLC) coupled with a UV/Vis photodiode detector. We found that in most cases, levels of aldehydes and methyl ethyl ketone (MEK) were significantly higher (2–125 times) in exhaled e-cigarette breaths than in pre-exposed breath. Exposure levels for the most abundant individual carbonyls in e-cigarette emissions—formaldehyde, acetaldehyde, acrolein—were between the limit of quantification (LOQ) and 24.4 μg·puff−1. The mean retention of formaldehyde in the respiratory tract was 99.7 ± 0.9% for all participants, while acetaldehyde retention was 91.6 ± 9.9%. Within the limitation of a small number of participants, our results showed that there is an increase in breath carbonyls during e-cigarette use.
6 September 2018 in Aerosol Science and Technology
Semivolatile organic compounds (SVOCs) emitted from open biomass burning (BB) can contribute to chemical and physical properties of atmospheric aerosols and also may cause adverse health effects. The polar fraction of SVOCs is a prominent part of BB organic aerosols, and thus it is important to characterize the chemical composition and reactivity of this fraction. In this study, globally and regionally important representative fuels (Alaskan peat, Moscow peat, Pskov peat, eucalyptus, Malaysian peat, and Malaysian agricultural peat) were burned under controlled conditions using the combustion chamber facility at the Desert Research Institute (DRI). Gas- and particle-phase biomass-burning emissions were aged in an oxidation flow reactor (OFR) to mimic 5–7 d of atmospheric aging. Fresh and OFR-aged biomass-burning aerosols were collected on Teflon-impregnated glass fiber filters (TIGF) in tandem with XAD resin media for organic carbon speciation. The polar fraction extracted with dichloromethane and acetone was analyzed with gas chromatography mass spectrometry (GC-MS) for 84 polar organic compounds – including mono- and dicarboxylic acids, methoxylated phenols, aromatic acids, anhydrosugars, resin acids, and sterols. For all these compounds, fuel-based emission factors (EFs) were calculated for fresh and OFR-aged samples. The carbon mass of the quantified polar compounds was found to constitute 5 % to 7 % of the total organic compound mass. A high abundance of methoxyphenols (239 mg kg−1 for Pskov peat; 22.6 % of total GC-MS characterized mass) and resin acids (118 mg kg−1 for Alaskan peat; 14.5 % of total GC-MS characterized mass) was found in peat-burning emissions (smoldering combustion). The concentration of some organic compounds (e.g., tetracosanoic acid) with a molecular weight (MW) above 350 g mol−1 decreased after OFR aging, while abundances of low-MW compounds (e.g., hexanoic acid) increased. This indicated a significant extent of fragmentation reactions in the OFR. Methoxyphenols decreased after OFR aging, while a significant increase (3.7 to 8.6 times) in the abundance of dicarboxylic acids emission factors (EFs), especially maleic acid (10 to 60 times), was observed. EFs for fresh and ratios from fresh-to-aged BB samples reported in this study can be used to perform source apportionment and predict processes occurring during atmospheric transport.
Poor air quality arising from prescribed and wildfire smoke emissions poses threats to human health and therefore must be taken into account for the planning and implementation of prescribed burns for reducing contemporary fuel loading and other management goals. To better understand how smoke properties vary as a function of fuel beds and environmental conditions, we developed and tested a compact portable instrument package that integrates direct air sampling with air quality and meteorology sensing, suitable for in situ data collection within burn units and as a payload on multi-rotor small unmanned aircraft systems (sUASs). Co-located sensors collect carbon dioxide, carbon monoxide, and particulate matter data at a sampling rate of ~0.5 Hz with a microcontroller-based system that includes independent data logging, power systems, radio telemetry, and global positioning system data. Sensor data facilitates precise remote canister collection of air samples suitable for laboratory analysis of volatile organic compounds (VOCs) and other major and trace gases. Instrument package specifications are compatible with common protocols for ground-based and airborne measurements. We present and discuss design specifications for the system and preliminary data collected in controlled burns at Tall Timbers Research Station, FL, USA and Sycan Marsh Preserve, OR, USA.