Aerosolized Cyanobacterial Harmful Algal Bloom Toxins: Microcystin Congeners Quantified in the Atmosphere.

Cyanobacterial harmful algal blooms (cHABs) have the potential to adversely affect public health through the production of toxins such as microcystins, which consist of numerous molecularly distinct congeners. Microcystins have been observed in the atmosphere after emission from freshwater lakes, but little is known about the health effects of inhaling microcystins and the factors contributing to microcystin aerosolization. This study quantified total microcystin concentrations in water and aerosol samples collected around Grand Lake St. Marys (GLSM), Ohio. Microcystin concentrations in water samples collected on the same day ranged from 13 to 23 µg/L, dominated by the d-Asp3-MC-RR congener. In particulate matter <2.5 µm (PM2.5), microcystin concentrations up to 156 pg/m3 were detected; the microcystins were composed primarily of d-Asp3-MC-RR, with additional congeners (d-Asp3-MC-HtyR and d-Asp3-MC-LR) observed in a sample collected prior to a storm event. The PM size fraction containing the highest aerosolized MC concentration ranged from 0.44 to 2.5 µm. Analysis of total bacteria by qPCR targeting 16S rDNA revealed concentrations up to 9.4 × 104 gc/m3 in aerosol samples (≤3 µm), while a marker specific to cyanobacteria was not detected in any aerosol samples. Concentrations of aerosolized microcystins varied even when concentrations in water were relatively constant, demonstrating the importance of meteorological conditions (wind speed and direction) and aerosol generation mechanism(s) (wave breaking, spillway, and aeration systems) when evaluating inhalation exposure to microcystins and subsequent impacts on human health.

Wildfires Increase Concentrations of Hazardous Air Pollutants in Downwind Communities.

Due in part to climate change, wildfire activity is increasing, with the potential for greater public health impact from smoke in downwind communities. Studies examining the health effects of wildfire smoke have focused primarily on fine particulate matter (PM2.5), but there is a need to better characterize other constituents, such as hazardous air pollutants (HAPs). HAPs are chemicals known or suspected to cause cancer or other serious health effects that are regulated by the United States (US) Environmental Protection Agency. Here, we analyzed concentrations of 21 HAPs in wildfire smoke from 2006 to 2020 at 309 monitors across the western US. Additionally, we examined HAP concentrations measured in a major population center (San Jose, CA) affected by multiple fires from 2017 to 2020. We found that concentrations of select HAPs, namely acetaldehyde, acrolein, chloroform, formaldehyde, manganese, and tetrachloroethylene, were all significantly elevated on smoke-impacted versus nonsmoke days (P < 0.05). The largest median increase on smoke-impacted days was observed for formaldehyde, 1.3 µg/m3 (43%) higher than that on nonsmoke days. Acetaldehyde increased 0.73 µg/m3 (36%), and acrolein increased 0.14 µg/m3 (34%). By better characterizing these chemicals in wildfire smoke, we anticipate that this research will aid efforts to reduce exposures in downwind communities.

Wildfires in the western United States are mobilizing PM2.5-associated nutrients and may be contributing to downwind cyanobacteria blooms.

Wildfire activity is increasing in the continental U.S. and can be linked to climate change effects, including rising temperatures and more frequent drought conditions. Wildfire emissions and large fire frequency have increased in the western U.S., impacting human health and ecosystems. We linked 15 years (2006-2020) of particulate matter (PM2.5) chemical speciation data with smoke plume analysis to identify PM2.5-associated nutrients elevated in air samples on smoke-impacted days. Most macro- and micro-nutrients analyzed (phosphorus, calcium, potassium, sodium, silicon, aluminum, iron, manganese, and magnesium) were significantly elevated on smoke days across all years analyzed. The largest percent increase was observed for phosphorus. With the exception of ammonium, all other nutrients (nitrate, copper, and zinc), although not statistically significant, had higher median values across all years on smoke vs. non-smoke days. Not surprisingly, there was high variation between smoke impacted days, with some nutrients episodically elevated >10 000% during select fire events. Beyond nutrients, we also explored instances where algal blooms occurred in multiple lakes downwind from high-nutrient fires. In these cases, remotely sensed cyanobacteria indices in downwind lakes increased two to seven days following the occurrence of wildfire smoke above the lake. This suggests that elevated nutrients in wildfire smoke may contribute to downwind algal blooms. Since cyanobacteria blooms can be associated with the production of cyanotoxins and wildfire activity is increasing due to climate change, this finding has implications for drinking water reservoirs in the western United States, and for lake ecology, particularly alpine lakes with otherwise limited nutrient inputs.

Initial pH Governs Secondary Organic Aerosol Phase State and Morphology after Uptake of Isoprene Epoxydiols (IEPOX).

Aerosol acidity increases secondary organic aerosol (SOA) formed from the reactive uptake of isoprene-derived epoxydiols (IEPOX) by enhancing condensed-phase reactions within sulfate-containing submicron particles, leading to low-volatility organic products. However, the link between the initial aerosol acidity and the resulting physicochemical properties of IEPOX-derived SOA remains uncertain. Herein, we show distinct differences in the morphology, phase state, and chemical composition of individual organic-inorganic mixed particles after IEPOX uptake to ammonium sulfate particles with different initial atmospherically relevant acidities (pH = 1, 3, and 5). Physicochemical properties were characterized via atomic force microscopy coupled with photothermal infrared spectroscopy (AFM-PTIR) and Raman microspectroscopy. Compared to less acidic particles (pH 3 and 5), reactive uptake of IEPOX to the most acidic particles (pH 1) resulted in 50% more organosulfate formation, clearer phase separation (core-shell), and more irregularly shaped morphologies, suggesting that the organic phase transitioned to semisolid or solid. This study highlights that initial aerosol acidity may govern the subsequent aerosol physicochemical properties, such as viscosity and morphology, following the multiphase chemical reactions of IEPOX. These results can be used in future studies to improve model parameterizations of SOA formation from IEPOX and its properties, toward the goal of bridging predictions and atmospheric observations.

Wildfire Smoke Influence on Cloud Water Chemical Composition at Whiteface Mountain, New York.

Wildfires significantly impact air quality and climate, including through the production of aerosols that can nucleate cloud droplets and participate in aqueous-phase reactions. Cloud water was collected during the summer months (June-September) of 2010-2017 at Whiteface Mountain, New York and examined for biomass burning influence. Cloud water samples were classified by their smoke influence based on backward air mass trajectories and satellite-detected smoke. A total of 1,338 cloud water samples collected over 485 days were classified by their probability of smoke influence, with 49% of these days categorized as having moderate to high probability of smoke influence. Carbon monoxide and ozone levels were enhanced during smoke influenced days at the summit of Whiteface Mountain. Smoke-influenced cloud water samples were characterized by enhanced concentrations of potassium, sulfate, ammonium, and total organic carbon, compared to samples lacking identified influence. Five cloud water samples were examined further for the presence of dissolved organic compounds, insoluble particles, and light-absorbing components. The five selected cloud water samples contained the biomass burning tracer levoglucosan at 0.02-0.09 µM. Samples influenced by air masses that remained aloft, above the boundary layer during transport, had lower insoluble particle concentrations, larger insoluble particle diameters, and larger oxalate:sulfate ratios, suggesting cloud processing had occurred. These findings highlight the influence that local and long-range transported smoke have on cloud water composition.

Simultaneous Optical Photothermal Infrared (O-PTIR) and Raman Spectroscopy of Submicrometer Atmospheric Particles.

Physicochemical analysis of individual atmospheric aerosols at the most abundant sizes in the atmosphere (<1 µm) is analytically challenging, as hundreds to thousands of species are often present in femtoliter volumes. Vibrational spectroscopies, such as infrared (IR) and Raman, have great potential for probing functional groups in single particles at ambient pressure and temperature. However, the diffraction limit of IR radiation limits traditional IR microscopy to particles > ∼10 µm, which have less relevance to aerosol health and climate impacts. Optical photothermal infrared (O-PTIR) spectroscopy is a contactless method that circumvents diffraction limitations by using changes in the scattering intensity of a continuous wave visible laser (532 nm) to detect the photothermal expansion when a vibrational mode is excited by a tunable IR laser (QCL: 800-1800 cm-1 or OPO: 2600-3600 cm-1). Herein, we simultaneously collect O-PTIR spectra with Raman spectra at a single point for individual particles with aerodynamic diameters <400 nm (prior to impaction and spreading) at ambient temperature and pressure, by also collecting the inelastically scattered visible photons for Raman spectra. O-PTIR and Raman spectra were collected for submicrometer particles with different substrates, particle chemical compositions, and morphologies (i.e., core-shell), as well as IR mapping with submicron spatial resolution. Initial O-PTIR analysis of ambient atmospheric particles identified both inorganic and organic modes in individual sub- and supermicrometer particles. The simultaneous IR and Raman microscopy with submicrometer spatial resolution described herein has considerable potential both in atmospheric chemistry and numerous others fields (e.g., materials and biological research).

Aerosol Acidity Sensing via Polymer Degradation.

The acidity of atmospheric aerosols is a critical property that affects the chemistry and composition of the atmosphere. Many key multiphase chemical reactions are pH-dependent, impacting processes like secondary organic aerosol formation, and need to be understood at a single particle level due to differences in particle-to-particle composition that impact both climate and health. However, the analytical challenge of measuring aerosol acidity in individual particles has limited pH measurements for fine (<2.5 µm) and coarse (2.5-10 µm) particles. This has led to a reliance on indirect methods or thermodynamic modeling, which focus on average, not individual, particle pH. Thus, new approaches are needed to probe single particle pH. In this study, a novel method for pH measurement was explored using degradation of a pH-sensitive polymer, poly(ε-caprolactone), to determine the acidity of individual submicron particles. Submicron particles of known pH (0 or 6) were deposited on a polymer film (21-25 nm thick) and allowed to react. Particles were then rinsed off, and the degradation of the polymer was characterized using atomic force microscopy and Raman microspectroscopy. After degradation, holes in the PCL films exposed to pH 0 were observed, and the loss of the carbonyl stretch was monitored at 1723 cm-1. As particle size decreased, polymer degradation increased, indicating an increase in aerosol acidity at smaller particle diameters. This study describes a new approach to determine individual particle acidity and is a step toward addressing a key measurement gap related to our understanding of atmospheric aerosol impacts on climate and health.

Harmful Algal Bloom Toxins in Aerosol Generated from Inland Lake Water.

Harmful algal blooms (HABs) caused by cyanobacteria in freshwater environments produce toxins (e.g., microcystin) that are harmful to human and animal health. HAB frequency and intensity are increasing with greater nutrient runoff and a warming climate. Lake spray aerosol (LSA) released from freshwater lakes has been identified on lakeshores and after transport inland, including from lakes with HABs, but little is known about the potential for HAB toxins to be incorporated into LSA. In this study, freshwater samples were collected from two lakes in Michigan: Mona Lake during a severe HAB with microcystin concentrations (>200 µg/L) well above the Environmental Protection Agency (EPA) recommended "do not drink" level (1.6 µg/L) and Muskegon Lake without a HAB (<1 µg/L microcystin). Microcystin toxins were identified in freshwater, as well as aerosol particles generated in the laboratory from Mona Lake water by liquid chromatography-tandem mass spectrometry (LC-MS/MS) at atmospheric concentrations up to 50 ± 20 ng/m3. Enrichment of hydrophobic microcystin congeners (e.g., microcystin-LR) was observed in aerosol particles relative to bulk freshwater, while enrichment of hydrophilic microcystin (e.g., microcystin-RR) was lower. As HABs increase in a warming climate, understanding and quantifying the emissions of toxins into the atmosphere is crucial for evaluating the health consequences of HABs.

Increasing Isoprene Epoxydiol-to-Inorganic Sulfate Aerosol Ratio Results in Extensive Conversion of Inorganic Sulfate to Organosulfur Forms: Implications for Aerosol Physicochemical Properties.

Acid-driven multiphase chemistry of isoprene epoxydiols (IEPOX), key isoprene oxidation products, with inorganic sulfate aerosol yields substantial amounts of secondary organic aerosol (SOA) through the formation of organosulfur compounds. The extent and implications of inorganic-to-organic sulfate conversion, however, are unknown. In this article, we demonstrate that extensive consumption of inorganic sulfate occurs, which increases with the IEPOX-to-inorganic sulfate concentration ratio (IEPOX/Sulfinorg), as determined by laboratory measurements. Characterization of the total sulfur aerosol observed at Look Rock, Tennessee, from 2007 to 2016 shows that organosulfur mass fractions will likely continue to increase with ongoing declines in anthropogenic Sulfinorg, consistent with our laboratory findings. We further demonstrate that organosulfur compounds greatly modify critical aerosol properties, such as acidity, morphology, viscosity, and phase state. These new mechanistic insights demonstrate that changes in SO2 emissions, especially in isoprene-dominated environments, will significantly alter biogenic SOA physicochemical properties. Consequently, IEPOX/Sulfinorg will play an important role in understanding the historical climate and determining future impacts of biogenic SOA on the global climate and air quality.

Bouncier Particles at Night: Biogenic Secondary Organic Aerosol Chemistry and Sulfate Drive Diel Variations in the Aerosol Phase in a Mixed Forest.

Aerosol phase state is critical for quantifying aerosol effects on climate and air quality. However, significant challenges remain in our ability to predict and quantify phase state during its evolution in the atmosphere. Herein, we demonstrate that aerosol phase (liquid, semisolid, solid) exhibits a diel cycle in a mixed forest environment, oscillating between a viscous, semisolid phase state at night and liquid phase state with phase separation during the day. The viscous nighttime particles existed despite higher relative humidity and were independently confirmed by bounce factor measurements and atomic force microscopy. High-resolution mass spectrometry shows the more viscous phase state at night is impacted by the formation of terpene-derived and higher molecular weight secondary organic aerosol (SOA) and smaller inorganic sulfate mass fractions. Larger daytime particulate sulfate mass fractions, as well as a predominance of lower molecular weight isoprene-derived SOA, lead to the liquid state of the daytime particles and phase separation after greater uptake of liquid water, despite the lower daytime relative humidity. The observed diel cycle of aerosol phase should provoke rethinking of the SOA atmospheric lifecycle, as it suggests diurnal variability in gas-particle partitioning and mixing time scales, which influence aerosol multiphase chemistry, lifetime, and climate impacts.

Extending surface enhanced Raman spectroscopy (SERS) of atmospheric aerosol particles to the accumulation mode (150-800 nm).

Due to their small size, measurements of the complex composition of atmospheric aerosol particles and their surfaces are analytically challenging. This is particularly true for microspectroscopic methods, where it can be difficult to optically identify individual particles smaller than the diffraction limit of visible light (∼350 nm) and measure their vibrational modes. Recently, surface enhanced Raman spectroscopy (SERS) has been applied to the study of aerosol particles, allowing for detection and characterization of previously undistinguishable vibrational modes. However, atmospheric particles analyzed via SERS have primarily been >1 µm to date, much larger than the diameter of the most abundant atmospheric aerosols (∼100 nm). To push SERS towards more relevant particle sizes, a simplified approach involving Ag foil substrates was developed. Both ambient particles and several laboratory-generated model aerosol systems (polystyrene latex spheres (PSLs), ammonium sulfate, and sodium nitrate) were investigated to determine SERS enhancements. SERS spectra of monodisperse, model aerosols between 400-800 nm were compared with non-SERS enhanced spectra, yielding average enhancement factors of 102 for both inorganic and organic vibrational modes. Additionally, SERS-enabled detection of 150 nm size-selected ambient particles represent the smallest individual aerosol particles analyzed by Raman microspectroscopy to date, and the first time atmospheric particles have been measured at sizes approaching the atmospheric number size distribution mode. SERS-enabled detection and identification of vibrational modes in smaller, more atmospherically-relevant particles has the potential to improve understanding of aerosol composition and surface properties, as well as their impact on heterogeneous and multiphase reactions involving aerosol surfaces.

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.