Overview of the Alaskan Layered Pollution and Chemical Analysis (ALPACA) Field Experiment.

The Alaskan Layered Pollution And Chemical Analysis (ALPACA) field experiment was a collaborative study designed to improve understanding of pollution sources and chemical processes during winter (cold climate and low-photochemical activity), to investigate indoor pollution, and to study dispersion of pollution as affected by frequent temperature inversions. A number of the research goals were motivated by questions raised by residents of Fairbanks, Alaska, where the study was held. This paper describes the measurement strategies and the conditions encountered during the January and February 2022 field experiment, and reports early examples of how the measurements addressed research goals, particularly those of interest to the residents. Outdoor air measurements showed high concentrations of particulate matter and pollutant gases including volatile organic carbon species. During pollution events, low winds and extremely stable atmospheric conditions trapped pollution below 73 m, an extremely shallow vertical scale. Tethered-balloon-based measurements intercepted plumes aloft, which were associated with power plant point sources through transport modeling. Because cold climate residents spend much of their time indoors, the study included an indoor air quality component, where measurements were made inside and outside a house to study infiltration and indoor sources. In the absence of indoor activities such as cooking and/or heating with a pellet stove, indoor particulate matter concentrations were lower than outdoors; however, cooking and pellet stove burns often caused higher indoor particulate matter concentrations than outdoors. The mass-normalized particulate matter oxidative potential, a health-relevant property measured here by the reactivity with dithiothreiol, of indoor particles varied by source, with cooking particles having less oxidative potential per mass than pellet stove particles.

Amine Volatilization from Herbicide Salts: Implications for Herbicide Formulations and Atmospheric Chemistry.

Amines are frequently included in formulations of the herbicides glyphosate, 2,4-D, and dicamba to increase herbicide solubility and reduce herbicide volatilization by producing herbicide-amine salts. Amines, which typically have higher vapor pressures than the corresponding herbicides, could potentially volatilize from these salts and enter the atmosphere, where they may impact atmospheric chemistry, human health, and climate. Amine volatilization from herbicide-amine salts may additionally contribute to volatilization of dicamba and 2,4-D. In this study, we established that amines applied in herbicide-amine salt formulations undergo extensive volatilization. Both dimethylamine and isopropylamine volatilized when aqueous salt solutions were dried to a residue at ∼20 °C, while lower-vapor pressure amines like diglycolamine and n,n-bis-(3-aminopropyl)methylamine did not. However, all four amines volatilized from salt residues at 40-80 °C. Because amine loss typically exceeded herbicide loss, we proposed that neutral amines dominated volatilization and that higher temperatures altered their protonation state and vapor pressure. Due to an estimated 4.0 Gg N/yr applied as amines to major U.S. crops, amine emissions from herbicide-amine salts may be important on regional scales. Further characterization of worldwide herbicide-amine use would enable this contribution to be compared to the 285 Gg N/yr of methylamines emitted globally.

Herbicide Drift from Genetically Engineered Herbicide-Tolerant Crops.

In recent years, off-target herbicide drift has been increasingly reported to lead to damage to nontarget vegetation in the U.S. These reports have coincided with the widespread adoption of genetically modified crops with new herbicide-tolerance traits. Planting crops with these traits may indirectly lead to increased drift both by increasing the use of the corresponding herbicides and by facilitating their use as postemergence herbicides later in the season. While extensive efforts have aimed to reduce herbicide drift, critical uncertainties remain regarding the physiochemical phenomena that drive the entry of herbicides into the atmosphere as well as the atmospheric processes that may influence short- and long-range transport. Resolving these uncertainties will support the development of effective approaches to reduce herbicide drift.

Protection levels of N95-level respirator substitutes proposed during the COVID-19 pandemic: safety concerns and quantitative evaluation procedures.

OBJECTIVE: The COVID-19 pandemic has precipitated widespread shortages of filtering facepiece respirators (FFRs) and the creation and sharing of proposed substitutes (novel designs, repurposed materials) with limited testing against regulatory standards. We aimed to categorically test the efficacy and fit of potential N95 respirator substitutes using protocols that can be replicated in university laboratories. SETTING: Academic medical centre with occupational health-supervised fit testing along with laboratory studies. PARTICIPANTS: Seven adult volunteers who passed quantitative fit testing for small-sized (n=2) and regular-sized (n=5) commercial N95 respirators. METHODS: Five open-source potential N95 respirator substitutes were evaluated and compared with commercial National Institute for Occupational Safety and Health (NIOSH)-approved N95 respirators as controls. Fit testing using the 7-minute standardised Occupational Safety and Health Administration fit test was performed. In addition, protocols that can be performed in university laboratories for materials testing (filtration efficiency, air resistance and fluid resistance) were developed to evaluate alternate filtration materials. RESULTS: Among five open-source, improvised substitutes evaluated in this study, only one (which included a commercial elastomeric mask and commercial HEPA filter) passed a standard quantitative fit test. The four alternative materials evaluated for filtration efficiency (67%-89%) failed to meet the 95% threshold at a face velocity (7.6 cm/s) equivalent to that of a NIOSH particle filtration test for the control N95 FFR. In addition, for all but one material, the small surface area of two 3D-printed substitutes resulted in air resistance that was above the maximum in the NIOSH standard. CONCLUSIONS: Testing protocols such as those described here are essential to evaluate proposed improvised respiratory protection substitutes, and our testing platform could be replicated by teams with similar cross-disciplinary research capacity. Healthcare professionals should be cautious of claims associated with improvised respirators when suggested as FFR substitutes.

Evaluating Indoor Air Chemical Diversity, Indoor-to-Outdoor Emissions, and Surface Reservoirs Using High-Resolution Mass Spectrometry.

Detailed offline speciation of gas- and particle-phase organic compounds was conducted using gas/liquid chromatography with traditional and high-resolution mass spectrometers in a hybrid targeted/nontargeted analysis. Observations were focused on an unoccupied home and were compared to two other indoor sites. Observed gas-phase organic compounds span the volatile to semivolatile range, while functionalized organic aerosols extend from intermediate volatility to ultra-low volatility, including a mix of oxygen, nitrogen, and sulfur-containing species. Total gas-phase abundances of hydrocarbon and oxygenated gas-phase complex mixtures were elevated indoors and strongly correlated in the unoccupied home. While gas-phase concentrations of individual compounds generally decreased slightly with greater ventilation, their elevated ratios relative to controlled emissions of tracer species suggest that the dilution of gas-phase concentrations increases off-gassing from surfaces and other indoor reservoirs, with volatility-dependent responses to dynamically changing environmental factors. Indoor-outdoor emissions of gas-phase intermediate-volatility/semivolatile organic hydrocarbons from the unoccupied home averaged 6-11 mg h-1, doubling with ventilation. While the largest single-compound emissions observed were furfural (61-275 mg h-1) and acetic acid, observations spanned a wide range of individual volatile chemical products (e.g., terpenoids, glycol ethers, phthalates, other oxygenates), highlighting the abundance of long-lived reservoirs resulting from prior indoor use or materials, and their gradual transport outdoors.

Size-Dependent Filtration Efficiency of Alternative Facemask Filter Materials.

The use of facemasks is proven to mitigate the spread of the coronavirus and other biological agents that cause disease. Various forms of facemasks, made using different materials, are being used extensively, and it is important to determine their performance characteristics. The size-dependent filtration efficiency and breathing resistance of household sterilization wrap fabrics, and isolation media (American Society for Testing and Materials (ASTM)- and non-ASTM-rated), were measured in filter-holder- and mannequin-in-chamber-based systems, focusing on particles sizes between 20 nm and 2 µm. Double-layer MERV-14 (Minimum Efficiency Reporting Values with rating 14) showed the highest filtration efficiency (94.9-73.3%) amongst household filter media, whereas ASTM-rated isolation masks showed the highest filtration efficiencies (95.6-88.7) amongst all the masks considered. Filtration efficiency of 3D-printed masks with replaceable filter media was found to depend on the degree of sealing around the media holder, which depended on the material's compressibility. Filtration efficiencies of triple-layer combinations (95.8-85.3%) follow a profile similar to single layers but with improved filtration efficiencies.

Continuous measurement of reactive oxygen species inside and outside of a residential house during summer.

Reactive oxygen species (ROS) are an important contributor to adverse health effects associated with ambient air pollution. Despite infiltration of ROS from outdoors, and possible indoor sources (eg, combustion), there are limited data available on indoor ROS. In this study, part of the second phase of Air Composition and Reactivity from Outdoor aNd Indoor Mixing campaign (ACRONIM-2), we constructed and deployed an online, continuous, system to measure extracellular gas- and particle-phase ROS during summer in an unoccupied residence in St. Louis, MO, USA. Over a period of one week, we observed that the non-denuded outdoor ROS (representing particle-phase ROS and some gas-phase ROS) concentration ranged from 1 to 4 nmol/m3 (as H2 O2 ). Outdoor concentrations were highest in the afternoon, coincident with peak photochemistry periods. The indoor concentrations of particle-phase ROS were nearly equal to outdoor concentrations, regardless of window-opening status or air exchange rates. The indoor/outdoor ratio of non-denuded ROS (I/OROS ) was significantly less than 1 with windows open and even lower with windows closed. Combined, these observations suggest that gas-phase ROS are efficiently removed by interior building surfaces and that there may be an indoor source of particle-phase ROS.

Density and Homogeneous Internal Composition of Primary Brown Carbon Aerosol.

The presence of atmospheric brown carbon (BrC) has been the focus of many recent studies. These particles, predominantly emitted from smoldering biomass burning, absorb light in the near-ultraviolet and short visible wavelengths and offset the radiative cooling effects associated with organic aerosols. Particle density dictates their transport properties and is an important parameter in climate models and aerosol instrumentation algorithms, but our knowledge of this particle property is limited, especially as functions of combustion temperature and fuel type. We measured the effective density (ρeff) and optical properties of primary BrC aerosol emitted from smoldering combustion of Boreal peatlands. Energy transfer into the fuel was controlled by selectively altering the combustion ignition temperature, and we find that the particle ρeff ranged from 0.85 to 1.19 g cm-3 corresponding to ignition temperatures from 180 to 360 °C. BrC particles exhibited spherical morphology and a constant 3.0 mass-mobility exponent, indicating no internal microstructure or void spaces. Upon partial thermal volatilization, ρeff of the remaining particle mass was confined to a narrow range between 0.9 and 1.1 g cm-3. These findings lead us to conclude that primary BrC aerosols from biomass burning have homogeneous internal composition, and their ρeff is in fact their actual density.

Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol.

Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry-climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

Nighttime Chemistry and Morning Isoprene Can Drive Urban Ozone Downwind of a Major Deciduous Forest.

Isoprene is the predominant non-methane volatile organic compound emitted to the atmosphere and shapes tropospheric composition and biogeochemistry through its effects on ozone, other oxidants, aerosols, and the nitrogen cycle. Isoprene is emitted naturally by vegetation during daytime, when its photo-oxidation is rapid, and in the presence of nitrogen oxides (NOx) produces ozone and degrades air quality in polluted regions. Here, we show for a city downwind of an isoprene-emitting forest (St. Louis, MO) that isoprene actually peaks at night; ambient levels then endure, owing to low nighttime OH radical concentrations. Nocturnal chemistry controls the fate of that isoprene and the likelihood of a high-ozone episode the following day. When nitrate (NO3) radicals are suppressed, high isoprene persists through the night, providing photochemical fuel upon daybreak and leading to a dramatic late-morning ozone peak. On nights with significant NO3, isoprene is removed before dawn; days with low morning isoprene then have lower ozone with a more typical afternoon peak. This biogenic-anthropogenic coupling expands the daily high-ozone window and likely has an opposite O3-NOx response to what would otherwise be expected, with implications for exposure and air-quality management in cities that, like St. Louis, are downwind of major isoprene-emitting forests.

Electronic cigarettes: The nicotyrine hypothesis.

There are conflicting reports about the efficacy of electronic cigarettes (e-cigs) as nicotine delivery devices and smoking cessation products. In addition, smokers' responses to some nicotine dependence questions often change as they transition to exclusive e-cig use. Nicotyrine may explain these observations. Nicotyrine forms by the gradual oxidation of nicotine in e-liquids exposed to air. E-cigs aerosolize nicotyrine along with nicotine. Nicotyrine inhibits the cytochrome P450 2A family of enzymes (CYP2A) in airways and liver. These enzymes metabolize nicotine to cotinine, and then cotinine to trans 3-hydroxycotinine. In humans, nicotine is metabolized primarily by hepatic CYP2A6. We propose that e-cig users (vapers) achieve measurable serum nicotine levels when they inhale nicotine and nicotyrine together, because nicotyrine reversibly inhibits nicotine metabolism by CYP2A13 in airways. Consuming nicotyrine by any route should irreversibly inhibit hepatic CYP2A6. When CYP2A6 is substantially inhibited, nicotine clearance is delayed and nicotine withdrawal symptoms are attenuated. Small, relatively infrequent nicotine doses can then sustain satisfying nicotine levels. This theory has numerous implications for e-cig research and tobacco control. Behavioral and pharmacokinetic e-cig studies should be interpreted with attention to likely levels of nicotyrine delivery: e-cig studies may need to routinely measure nicotyrine exposure, assess CYP2A6 activity, confirm nicotine delivery, or deliberately compare unoxidized and oxidized e-liquids. The risks of nicotyrine exposure include impaired clearance of all CYP2A substrates and any effects of the metabolic products of nicotyrine. CYP2A inhibitors like nicotyrine may be useful for future smoking cessation therapy.

Characteristics of particulate matter emissions from toy cars with electric motors.

UNLABELLED: Aerosol emissions from toy cars with electric motors were characterized. Particle emission rates from the toy cars, as high as 7.47×10(7) particles/s, were measured. This emission rate is lower than other indoor sources such as smoking and cooking. The particles emitted from toy cars are generated from spark discharges inside the electric motors that power the toy cars. Size distribution measurements indicated that most particles were below 100 nm in diameter. Copper was the dominant inorganic species in these particles. By deploying aerosol mass spectrometers, high concentrations of particulate organic matter were also detected and characterized in detail. Several organic compounds were identified using a thermal desorption aerosol gas chromatography. The mass size distribution of particulate organic matter was bimodal. The formation mechanism of particulate organic matter from toy cars was elucidated. IMPLICATIONS: A possible new source of indoor air pollution, particles from electric motors in toy cars, was identified. This study characterized aerosol emissions from toy cars in detail. Most of these particles have a diameter less than 100 nm. Copper and some organics are the major components of these particles. Conditions that minimize these emissions were determined.

On-Line Chemical Composition Analysis of Refillable Electronic Cigarette Aerosol-Measurement of Nicotine and Nicotyrine.

INTRODUCTION: Electronic cigarettes (e-cigs) generate aerosols that users inhale. Analyses of e-liquids inconsistently report nicotyrine, a nicotine analog that could impede nicotine metabolism, raising questions about nicotyrine formation. METHODS: E-cig aerosols were analyzed on-line using a Thermal Desorption Aerosol Gas Chromatograph. Three e-liquids were tested: an unflavored solution in propylene glycol (PG); an unflavored solution in PG and vegetable glycerin (VG), and a flavored solution in PG and VG. A heating duration experiment determined the nicotyrine to nicotine ratio (NNR) in particle phase as a function of the duration of e-cig activation. An aging experiment determined the NNR in e-liquids and aerosols as a function of time since initial exposure to air and storage condition. RESULTS: Nicotine and nicotyrine were quantified in all 3 e-liquids and aerosols. Duration of e-cig activation was inversely related to NNR (NNR = 0.04 with 3-s activation, 0.26 with 0.5 s). Aging influenced both e-liquid NNR and aerosol NNR. On average, the e-liquid NNR increased from 0.03 at 11 days after opening to 0.08 after 60 days. For similar heating durations, aerosol NNR increased from 0.05 at 11 days to 0.23 after 60 days. Storage conditions had little effect on NNR. CONCLUSIONS: E-cig aerosols have variable nicotyrine quantities. Aerosol NNR depends on vaping technique and time elapsed since the e-liquid was exposed to air. It is hypothesized that aerosolized nicotyrine could facilitate nicotine absorption, inhibit the metabolism of nicotine, and reduce a user's urge to smoke.

Development of a new consumable-free thermal modulator for comprehensive two-dimensional gas chromatography.

A simple and cost-effective GC×GC modulator requiring no moving parts or consumables, hence suitable for field analysis and monitoring, was developed. The modulator was constructed from a specially designed Silcosteel® trapping capillary, installed outside the GC oven, and coated inside with polydimethylsiloxane (PDMS) stationary phase. Dual-stage modulation was accomplished by resistively heating alternate segments of the trap with a custom-designed capacitive discharge power supply. The performance of the proposed modulator was comparable to many GC×GC systems currently in use, with the injection band widths as low as 60 ms at half height. With proper selection of the stationary phase in the trap, the modulator can be used for the analysis of complex mixtures with volatility range spanning from n-C5 to n-C40.

In situ measurements of gas/particle-phase transitions for atmospheric semivolatile organic compounds.

An understanding of the gas/particle-phase partitioning of semivolatile compounds is critical in determining atmospheric aerosol formation processes and growth rates, which in turn affect global climate and human health. The Study of Organic Aerosol at Riverside 2005 campaign was performed to gain a better understanding of the factors responsible for aerosol formation and growth in Riverside, CA, a region with high concentrations of secondary organic aerosol formed through the phase transfer of low-volatility reaction products from the oxidation of precursor gases. We explore the ability of the thermal desorption aerosol gas chromatograph (TAG) to measure gas-to-particle-phase transitioning for several organic compound classes (polar and nonpolar) found in the ambient Riverside atmosphere by using in situ observations of several hundred semivolatile organic compounds. Here we compare TAG measurements to modeled partitioning of select semivolatile organic compounds. Although TAG was not designed to quantify the vapor phase of semivolatile organics, TAG measurements do distinguish when specific compounds are dominantly in the vapor phase, are dominantly in the particle phase, or have both phases present. Because the TAG data are both speciated and time-resolved, this distinction is sufficient to see the transition from vapor to particle phase as a function of carbon number and compound class. Laboratory studies typically measure the phase partitioning of semivolatile organic compounds by using pure compounds or simple mixtures, whereas hourly TAG phase partitioning measurements can be made in the complex mixture of thousands of polar/nonpolar and organic/inorganic compounds found in the atmosphere.

Observations of aminium salts in atmospheric nanoparticles and possible climatic implications.

We present laboratory studies and field observations that explore the role of aminium salt formation in atmospheric nanoparticle growth. These measurements were performed using the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) and Ultrafine Hygroscopicity Tandem Differential Mobility Analyzers. Laboratory measurements of alkylammonium-carboxylate salt nanoparticles show that these particles exhibit lower volatilities and only slightly lower hygroscopicities than ammonium sulfate nanoparticles. TDCIMS measurements of these aminium salts showed that the protonated amines underwent minimal decomposition during analysis, with detection sensitivities comparable to those of organic and inorganic deprotonated acids. TDCIMS observations made of a new particle formation event in an urban site in Tecamac, Mexico, clearly indicate the presence of protonated amines in 8-10 nm diameter particles accounting for about 47% of detected positive ions; 13 nm particles were hygroscopic with an average 90% RH growth factor of 1.42. Observations of a new particle formation event in a remote forested site in Hyytiälä, Finland, show the presence of aminium ions with deprotonated organic acids; 23% of the detected positive ions during this event are attributed to aminium salts while 10 nm particles had an average 90% RH growth factor of 1.27. Similar TDCIMS observations during events in Atlanta and in the vicinity of Boulder, Colorado, show that aminium salts accounted for 10-35% of detected positive ions. We conclude that aminium salts contribute significantly to nanoparticle growth and must be accounted for in models to accurately predict the impact of new particle formation on climate.

Thermal desorption comprehensive two-dimensional gas chromatography for in-situ measurements of organic aerosols.

The complexity of organic composition and temporal variability of atmospheric aerosols presents an extreme analytical challenge. Comprehensive two-dimensional gas chromatography (GC x GC) has been used on time integrated filter samples to reveal the presence of thousands of individual organic compounds in aerosols, but without defining the temporal variability in composition ideal for providing information on source resolution and human exposure to specific pollutants. We hereby introduce a new instrument, 2D-TAG, which combines our in-situ thermal desorption aerosol GC (TAG) instrument with GC x GC allowing for dramatically improved separation of organics with automated measurements at hourly timescales.