Solid organic-coated ammonium sulfate particles at high relative humidity in the summertime Arctic atmosphere.

SignificancePhysical and chemical properties of individual atmospheric particles determine their climate impacts. Hygroscopic inorganic salt particles mixed with trace amounts of organic material are predicted to be liquid under typical tropospheric conditions in the summertime Arctic. Yet, we unexpectedly observed a significant concentration of solid particles composed of ammonium sulfate with an organic coating under conditions of high relative humidity and low temperature. These particle properties are consistent with marine biogenic-derived new particle formation and growth, with particle collision hypothesized to result in the solid phase. This particle source is predicted to have increasing relevance in the context of declining Arctic sea ice and increasing open water, with impacts on clouds, and therefore climate.

Residential Wood Burning and Vehicle Emissions as Major Sources of Environmentally Persistent Free Radicals in Fairbanks, Alaska.

Environmentally persistent free radicals (EPFRs) play an important role in aerosol effects on air quality and public health, but their atmospheric abundance and sources are poorly understood. We measured EPFRs contained in PM2.5 collected in Fairbanks, Alaska, in winter 2022. We find that EPFR concentrations were enhanced during surface-based inversion and correlate strongly with incomplete combustion markers, including carbon monoxide and elemental carbon (R2 > 0.75). EPFRs exhibit moderately good correlations with PAHs, biomass burning organic aerosols, and potassium (R2 > 0.4). We also observe strong correlations of EPFRs with hydrocarbon-like organic aerosols, Fe and Ti (R2 > 0.6), and single-particle mass spectrometry measurements reveal internal mixing of PAHs, with potassium and iron. These results suggest that residential wood burning and vehicle tailpipes are major sources of EPFRs and nontailpipe emissions, such as brake wear and road dust, may contribute to the stabilization of EPFRs. Exposure to the observed EPFR concentrations (18 ± 12 pmol m-3) would be equivalent to smoking ∼0.4-1 cigarette daily. Very strong correlations (R2 > 0.8) of EPFR with hydroxyl radical formation in surrogate lung fluid indicate that exposure to EPFRs may induce oxidative stress in the human respiratory tract.

Direct detection of atmospheric atomic bromine leading to mercury and ozone depletion.

Bromine atoms play a central role in atmospheric reactive halogen chemistry, depleting ozone and elemental mercury, thereby enhancing deposition of toxic mercury, particularly in the Arctic near-surface troposphere. However, direct bromine atom measurements have been missing to date, due to the lack of analytical capability with sufficient sensitivity for ambient measurements. Here we present direct atmospheric bromine atom measurements, conducted in the springtime Arctic. Measured bromine atom levels reached 14 parts per trillion (ppt, pmol mol-1; 4.2 × 108 atoms per cm-3) and were up to 3-10 times higher than estimates using previous indirect measurements not considering the critical role of molecular bromine. Observed ozone and elemental mercury depletion rates are quantitatively explained by the measured bromine atoms, providing field validation of highly uncertain mercury chemistry. Following complete ozone depletion, elevated bromine concentrations are sustained by photochemical snowpack emissions of molecular bromine and nitrogen oxides, resulting in continued atmospheric mercury depletion. This study provides a breakthrough in quantitatively constraining bromine chemistry in the polar atmosphere, where this chemistry connects the rapidly changing surface to pollutant fate.

The Role of Hydrates, Competing Chemical Constituents, and Surface Composition on ClNO2 Formation.

Atomic chlorine (Cl•) affects air quality and atmospheric oxidizing capacity. Nitryl chloride (ClNO2) - a common Cl• source-forms when chloride-containing aerosols react with dinitrogen pentoxide (N2O5). A recent study showed that saline lakebed (playa) dust is an inland source of particulate chloride (Cl-) that generates high ClNO2. However, the underlying physiochemical factors responsible for observed yields are poorly understood. To elucidate these controlling factors, we utilized single particle and bulk techniques to determine the chemical composition and mineralogy of playa sediment and dust samples from the southwest United States. Single particle analysis shows trace highly hygroscopic magnesium and calcium Cl-containing minerals are present and likely facilitate ClNO2 formation at low humidity. Single particle and mineralogical analysis detected playa sediment organic matter that hinders N2O5 uptake as well as 10 Å-clay minerals (e.g., Illite) that compete with water and chloride for N2O5. Finally, we show that the composition of the aerosol surface, rather than the bulk, is critical in ClNO2 formation. These findings underscore the importance of mixing state, competing reactions, and surface chemistry on N2O5 uptake and ClNO2 yield for playa dusts and, likely, other aerosol systems. Therefore, consideration of particle surface composition is necessary to improve ClNO2 and air quality modeling.

Diesel Soot and Amine-Containing Organic Sulfate Aerosols in an Arctic Oil Field.

The rapid decrease in Arctic sea ice is motivating development and increasing oil and gas extraction activities. However, few observations of these local Arctic emissions exist, limiting the understanding of impacts on atmospheric composition and climate. To address this knowledge gap, the chemical composition of atmospheric aerosols was measured within the North Slope of Alaska oil fields during August and September 2016 using an aerosol time-of-flight mass spectrometer (ATOFMS) and a time-of-flight aerosol chemical speciation monitor (ToF-ACSM). Plumes from oil and gas extraction activities were characterized by soot internally mixed with sulfate (matching diesel soot) and organic carbon particles containing aminium sulfate salts. Sea spray aerosol at the coastal site was frequently internally mixed with sulfate and nitrate, from multiphase chemical processing from elevated NOx and SO2 within the oil field. Background (nonplume) air masses were characterized by aged combustion aerosol. No periods of "clean" (nonpolluted) Arctic air were observed. The composition of the nonrefractory aerosol measured with the ACSM was similar during plume and background periods and was consistent with the mass concentrations of nonrefractory particles measured by ATOFMS. Two ultrafine aerosol growth events were observed during oil field background periods and were correlated with fine mode amine-containing particles.

Active molecular iodine photochemistry in the Arctic.

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I2) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I2 and snowpack iodide (I-) measurements, which were conducted near Utqiagvik, AK, in February 2014. Using chemical ionization mass spectrometry, I2 was observed in the atmosphere at mole ratios of 0.3-1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I- measurements showed enrichments of up to ∼1,900 times above the seawater ratio of I-/Na+, consistent with iodine activation and recycling. Modeling shows that observed I2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I2 is likely a dominant source of iodine atoms in the Arctic.

ClNO2 Production from N2O5 Uptake on Saline Playa Dusts: New Insights into Potential Inland Sources of ClNO2.

Nitryl chloride (ClNO2), formed when dinitrogen pentoxide (N2O5) reacts with chloride-containing aerosol, photolyzes to produce chlorine radicals that facilitate the formation of tropospheric ozone. ClNO2 has been measured in continental areas; however, the sources of particulate chloride required to form ClNO2 in inland regions remain unclear. Dust emitted from saline playas (e.g., dried lakebeds) contains salts that can potentially form ClNO2 in inland regions. Here, we present the first laboratory measurements demonstrating the production of ClNO2 from playa dusts. N2O5 reactive uptake coefficients (γN2O5) ranged from ∼10-3 to 10-1 and ClNO2 yields (φClNO2) were >50% for all playas tested except one. In general, as the soluble ion fraction of playa dusts increases, γN2O5 decreases and φClNO2 increases. We attribute this finding to a transition from aerosol surfaces dominated by silicates that react efficiently with N2O5 and produce little ClNO2 to aerosols that behave like deliquesced chloride-containing salts that generate high yields of ClNO2. Molecular bromine (Br2) and nitryl bromide (BrNO2) were also detected, highlighting that playas facilitate the heterogeneous production of brominated compounds. Our results suggest that parameterizations and models should be updated to include playas as an inland source of aerosol chloride capable of efficiently generating ClNO2.

Springtime Nitrogen Oxide-Influenced Chlorine Chemistry in the Coastal Arctic.

Atomic chlorine (Cl) is a strong atmospheric oxidant that shortens the lifetimes of pollutants and methane in the springtime Arctic, where the molecular halogens Cl2 and BrCl are known Cl precursors. Here, we quantify the contributions of reactive chlorine trace gases and present the first observations, to our knowledge, of ClNO2 (another Cl precursor), N2O5, and HO2NO2 in the Arctic. During March - May 2016 near Utqiagvik, Alaska, up to 21 ppt of ClNO2, 154 ppt of Cl2, 27 ppt of ClO, 71 ppt of N2O5, 21 ppt of BrCl, and 153 ppt of HO2NO2 were measured using chemical ionization mass spectrometry. The main Cl precursor was calculated to be Cl2 (up to 73%) in March, while BrCl was a greater contributor (63%) in May, when total Cl production was lower. Elevated levels of ClNO2, N2O5, Cl2, and HO2NO2 coincided with pollution influence from the nearby town of Utqiagvik and the North Slope of Alaska (Prudhoe Bay) Oilfields. We propose a coupled mechanism linking NOx with Arctic chlorine chemistry. Enhanced Cl2 was likely the result of the multiphase reaction of Cl-(aq) with ClONO2, formed from the reaction of ClO and NO2. In addition to this NOx-enhanced chlorine chemistry, Cl2 and BrCl were observed under clean Arctic conditions from snowpack photochemical production. These connections between NOx and chlorine chemistry, and the role of snowpack recycling, are important given increasing shipping and fossil fuel extraction predicted to accompany Arctic sea ice loss.

Aerosol Emissions from Great Lakes Harmful Algal Blooms.

In freshwater lakes, harmful algal blooms (HABs) of Cyanobacteria (blue-green algae) produce toxins that impact human health. However, little is known about the lake spray aerosol (LSA) produced from wave-breaking in freshwater HABs. In this study, LSA were produced in the laboratory from freshwater samples collected from Lake Michigan and Lake Erie during HAB and nonbloom conditions. The incorporation of biological material within the individual HAB-influenced LSA particles was examined by single-particle mass spectrometry, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and fluorescence microscopy. Freshwater with higher blue-green algae content produced higher number fractions of individual LSA particles that contained biological material, showing that organic molecules of biological origin are incorporated in LSA from HABs. The number fraction of individual LSA particles containing biological material also increased with particle diameter (greater than 0.5 µm), a size dependence that is consistent with previous studies of sea spray aerosol impacted by phytoplankton blooms. Similar to sea spray aerosol, organic carbon markers were most frequently observed in individual LSA particles less than 0.5 µm in diameter. Understanding the transfer of biological material from freshwater to the atmosphere via LSA is crucial for determining health and climate effects of HABs.

Atomic Force Microscopy-Infrared Spectroscopy of Individual Atmospheric Aerosol Particles: Subdiffraction Limit Vibrational Spectroscopy and Morphological Analysis.

Chemical analysis of atmospheric aerosols is an analytical challenge, as aerosol particles are complex chemical mixtures that can contain hundreds to thousands of species in attoliter volumes at the most abundant sizes in the atmosphere (∼100 nm). These particles have global impacts on climate and health, but there are few methods available that combine imaging and the detailed molecular information from vibrational spectroscopy for individual particles <500 nm. Herein, we show the first application of atomic force microscopy with infrared spectroscopy (AFM-IR) to detect trace organic and inorganic species and probe intraparticle chemical variation in individual particles down to 150 nm. By detecting photothermal expansion at frequencies where particle species absorb IR photons from a tunable laser, AFM-IR can study particles smaller than the optical diffraction limit. Combining strengths of AFM (ambient pressure, height, morphology, and phase measurements) with photothermal IR spectroscopy, the potential of AFM-IR is shown for a diverse set of single-component particles, liquid-liquid phase separated particles (core-shell morphology), and ambient atmospheric particles. The spectra from atmospheric model systems (ammonium sulfate, sodium nitrate, succinic acid, and sucrose) had clearly identifiable features that correlate with absorption frequencies for infrared-active modes. Additionally, molecular information was obtained with <100 nm spatial resolution for phase separated particles with a ∼150 nm shell and 300 nm core. The subdiffraction limit capability of AFM-IR has the potential to advance understanding of particle impacts on climate and health by improving analytical capabilities to study water uptake, heterogeneous reactivity, and viscosity.

Laboratory Studies of the Cloud Droplet Activation Properties and Corresponding Chemistry of Saline Playa Dust.

Playas emit large quantities of dust that can facilitate the activation of cloud droplets. Despite the potential importance of playa dusts for cloud formation, most climate models assume that all dust is nonhygroscopic; however, measurements are needed to clarify the role of dusts in aerosol-cloud interactions. Here, we report measurements of CCN activation from playa dusts and parameterize these results in terms of both κ-Köhler theory and adsorption activation theory for inclusion in atmospheric models. κ ranged from 0.002 ± 0.001 to 0.818 ± 0.094, whereas Frankel-Halsey-Hill (FHH) adsorption parameters of AFHH = 2.20 ± 0.60 and BFHH = 1.24 ± 0.14 described the water uptake properties of the dusts. Measurements made using aerosol time-of-flight mass spectrometry (ATOFMS) revealed the presence of halite, sodium sulfates, and sodium carbonates that were strongly correlated with κ underscoring the role that mineralogy, including salts, plays in water uptake by dust. Predictions of κ made using bulk chemical techniques generally showed good agreement with measured values. However, several samples were poorly predicted suggesting that chemical heterogeneities as a function of size or chemically distinct particle surfaces can determine the hygroscopicity of playa dusts. Our results further demonstrate the importance of dust in aerosol-cloud interactions.

Inland Sea Spray Aerosol Transport and Incomplete Chloride Depletion: Varying Degrees of Reactive Processing Observed during SOAS.

Multiphase reactions involving sea spray aerosol (SSA) impact trace gas budgets in coastal regions by acting as a reservoir for oxidized nitrogen and sulfur species, as well as being a source of halogen gases (HCl, ClNO2, etc.). Whereas most studies of multiphase reactions on SSA have focused on marine environments, far less is known about SSA transported inland. Herein, single-particle measurements of SSA are reported at a site >320 km from the Gulf of Mexico, with transport times of 7-68 h. Samples were collected during the Southern Oxidant and Aerosol Study (SOAS) in June-July 2013 near Centreville, Alabama. SSA was observed in 93% of 42 time periods analyzed. During two marine air mass periods, SSA represented significant number fractions of particles in the accumulation (0.2-1.0 µm, 11%) and coarse (1.0-10.0 µm, 35%) modes. Chloride content of SSA particles ranged from full to partial depletion, with 24% of SSA particles containing chloride (mole fraction of Cl/Na ≥ 0.1, 90% chloride depletion). Both the frequent observation of SSA at an inland site and the range of chloride depletion observed suggest that SSA may represent an underappreciated inland sink for NOx/SO2 oxidation products and a source of halogen gases.

Constraints on Arctic Atmospheric Chlorine Production through Measurements and Simulations of Cl2 and ClO.

During springtime, unique halogen chemistry involving chlorine and bromine atoms controls the prevalence of volatile organic compounds, ozone, and mercury in the Arctic lower troposphere. In situ measurements of the chlorine monoxide radical, ClO, and its precursor, Cl2, along with BrO and Br2, were conducted using chemical ionization mass spectrometry (CIMS) during the Bromine, Ozone, and Mercury Experiment (BROMEX) near Barrow, Alaska, in March 2012. To our knowledge, these data represent the first ClO measurements made using CIMS. A maximum daytime ClO concentration of 28 ppt was observed following an early morning peak of 75 ppt of Cl2. A zero-dimensional photochemistry model was constrained to Cl2 observations and used to simulate ClO during a 7-day period of the field campaign. The model simulates ClO within the measurement uncertainty, and the model results highlight the importance of chlorine chemistry participation in bromine radical cycling, as well as the dependence of halogen chemistry on NOx levels. The ClO measurements and simulations are consistent with Cl2 being the dominant Cl atom source in the Arctic boundary layer. Simulated Cl atom concentrations, up to ∼1 × 106 molecules cm-3, highlight the importance of chlorine chemistry in the degradation of volatile organic compounds, including the greenhouse gas methane.

Lake Spray Aerosol: A Chemical Signature from Individual Ambient Particles.

Aerosol production from wave breaking on freshwater lakes, including the Laurentian Great Lakes, is poorly understood in comparison to sea spray aerosol (SSA). Aerosols from freshwater have the potential to impact regional climate and public health. Herein, lake spray aerosol (LSA) is defined as aerosol generated from freshwater through bubble bursting, analogous to SSA from seawater. A chemical signature for LSA was determined from measurements of ambient particles collected on the southeastern shore of Lake Michigan during an event (July 6-8, 2015) with wave heights up to 3.1 m. For comparison, surface freshwater was collected, and LSA were generated in the laboratory. Single particle microscopy and mass spectrometry analysis of field and laboratory-generated samples show that LSA particles are primarily calcium (carbonate) with lower concentrations of other inorganic ions and organic material. Laboratory number size distributions show ultrafine and accumulation modes at 53 (±1) and 276 (±8) nm, respectively. This study provides the first chemical signature for LSA. LSA composition is shown to be coupled to Great Lakes water chemistry (Ca(2+) > Mg(2+) > Na(+) > K(+)) and distinct from SSA. Understanding LSA physicochemical properties will improve assessment of LSA impacts on regional air quality, climate, and health.

Aqueous Processing of Atmospheric Organic Particles in Cloud Water Collected via Aircraft Sampling.

Cloudwater and below-cloud atmospheric particle samples were collected onboard a research aircraft during the Southern Oxidant and Aerosol Study (SOAS) over a forested region of Alabama in June 2013. The organic molecular composition of the samples was studied to gain insights into the aqueous-phase processing of organic compounds within cloud droplets. High resolution mass spectrometry (HRMS) with nanospray desorption electrospray ionization (nano-DESI) and direct infusion electrospray ionization (ESI) were utilized to compare the organic composition of the particle and cloudwater samples, respectively. Isoprene and monoterpene-derived organosulfates and oligomers were identified in both the particles and cloudwater, showing the significant influence of biogenic volatile organic compound oxidation above the forested region. While the average O:C ratios of the organic compounds were similar between the atmospheric particle and cloudwater samples, the chemical composition of these samples was quite different. Specifically, hydrolysis of organosulfates and formation of nitrogen-containing compounds were observed for the cloudwater when compared to the atmospheric particle samples, demonstrating that cloud processing changes the composition of organic aerosol.

Enhanced aqueous formation and neutralization of fine atmospheric particles driven by extreme cold.

The prevailing view for aqueous secondary aerosol formation is that it occurs in clouds and fogs, owing to the large liquid water content compared to minute levels in fine particles. Our research indicates that this view may need reevaluation due to enhancements in aqueous reactions in highly concentrated small particles. Here, we show that low temperature can play a role through a unique effect on particle pH that can substantially modulate secondary aerosol formation. Marked increases in hydroxymethanesulfonate observed under extreme cold in Fairbanks, Alaska, demonstrate the effect. These findings provide insight on aqueous chemistry in fine particles under cold conditions expanding possible regions of secondary aerosol formation that are pH dependent beyond conditions of high liquid water.

Primary Sulfate Is the Dominant Source of Particulate Sulfate during Winter in Fairbanks, Alaska.

Within and surrounding high-latitude cities, poor air quality disturbs Arctic ecosystems, influences the climate, and harms human health. The Fairbanks North Star Borough has wintertime particulate matter (PM) concentrations that exceed the Environmental Protection Agency's (EPA) threshold for public health. Particulate sulfate (SO4 2-) is the most abundant inorganic species and contributes approximately 20% of the total PM mass in Fairbanks, but air quality models underestimate observed sulfate concentrations. Here we quantify sulfate sources using size-resolved δ34S(SO4 2-), δ18O(SO4 2-), and Δ17O(SO4 2-) of particulate sulfate in Fairbanks from January 18th to February 25th, 2022 using a Bayesian isotope mixing model. Primary sulfate contributes 62 ± 12% of the total sulfate mass on average. Most primary sulfate is found in the size bin with a particle diameter < 0.7 µm, which contains 90 ±5% of total sulfate mass and poses the greatest risk to human health. Oxidation by all secondary formation pathways combined contributes 38 ± 12% of total sulfate mass on average, indicating that secondary sulfate formation is inefficient in this cold, dark environment. On average, the dominant secondary sulfate formation pathways are oxidation by H2O2 (13 ± 6%), O3 (8 ± 4%), and NO2 (8 ± 3%). These findings will inform mitigation strategies to improve air quality and public health in Fairbanks and possibly other high-latitude urban areas during winter.

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.

Mass spectrometry of atmospheric aerosols--recent developments and applications. Part I: Off-line mass spectrometry techniques.

Many of the significant advances in our understanding of atmospheric particles can be attributed to the application of mass spectrometry. Mass spectrometry provides high sensitivity with a fast response time to probe chemically complex particles. This review focuses on recent developments and applications in the field of mass spectrometry of atmospheric aerosols. In Part I of this two-part review, we concentrate on off-line mass spectrometry techniques, which require sample collection on filters but can provide detailed molecular speciation. In particular, off-line mass spectrometry techniques utilizing tandem mass spectrometry experiments and high resolution mass analyzers provide improved insight into secondary organic aerosol formation and heterogeneous reaction pathways through detailed structural elucidation at the molecular level.

Mass spectrometry of atmospheric aerosols--recent developments and applications. Part II: On-line mass spectrometry techniques.

Many of the significant advances in our understanding of atmospheric particles can be attributed to the application of mass spectrometry. Mass spectrometry provides high sensitivity with fast response time to probe chemically complex particles. This review focuses on recent developments and applications in the field of mass spectrometry of atmospheric aerosols. In Part II of this two-part review, we concentrate on real-time mass spectrometry techniques, which provide high time resolution for insight into brief events and diurnal changes while eliminating the potential artifacts acquired during long-term filter sampling. In particular, real-time mass spectrometry has been shown recently to provide the ability to probe the chemical composition of ambient individual particles <30 nm in diameter to further our understanding of how particles are formed through nucleation in the atmosphere. Further, transportable real-time mass spectrometry techniques are now used frequently on ground-, ship-, and aircraft-based studies around the globe to further our understanding of the spatial distribution of atmospheric aerosols. In addition, coupling aerosol mass spectrometry techniques with other measurements in series has allowed the in situ determination of chemically resolved particle effective density, refractive index, volatility, and cloud activation properties.