Low-Cost Alternative for Online Analysis of Volatile Organic Compounds.

The use of online mass spectrometry for detecting volatile organic compounds (VOCs) has proven to be a powerful technique, allowing for real-time analysis of many chemical and biochemical processes. Unfortunately, online mass spectrometry has had limited application due to high instrument costs and limited availability. Here, we detail the design, construction, and performance characteristics of a custom ion-molecule reactor retrofitted to a commonly used single quadrupole mass spectrometer to operate as an online chemical ionization mass spectrometer (CIMS). This low-cost modified CIMS is capable of limits of detection below 10 parts per trillion for select VOCs including dimethyl sulfide, dimethylamine, and trimethylamine.

Effects of Relative Humidity and Phase on the Molecular Detection of Nascent Sea Spray Aerosol Using Extractive Electrospray Ionization.

Online mass spectrometry techniques, such as extractive electrospray ionization mass spectrometry (EESI-MS), present an attractive alternative for analyzing aerosol molecular composition due to reduced aerosol sample collection and handling times and improved time resolution. Recent studies show a dependence of EESI-MS sensitivity on particle size and mixing state. This study measured authentic sea spray aerosol (SSA) components generated during a phytoplankton bloom, specifically glycerol, palmitic acid, and potassium ions. We demonstrate temporal variability and trends dependent on specific biological processes occurring in seawater. We found that the EESI-MS sensitivity, after adjusting for pressure variations at the inlet and normalizing to the reagent ion, critically depends on the sample's relative humidity. Relevant SSA species exhibited heightened sensitivity at an elevated relative humidity near the deliquescence relative humidity of sea salt and poorer sensitivity with sparse detection below the efflorescence relative humidity. Modeling the reagent ion's diffusive depth demonstrates that the sample aerosol particle viscosity governs the relative humidity dependence because it modulates the particle's coagulation efficiency and distance the reagent ion diffuses and reacts with components in the particle bulk. The effects of particle size and mixing state are discussed, revealing improved sensitivity of phase-separated components present along the particle surface. This work highlights the importance of the particle phase state in detecting and quantifying molecular components within authentic and complex aerosol particles and the utility of EESI-MS for measuring SSA composition.

Sea-Air Transfer of Ostreopsis Phycotoxins Is Driven by the Chemical Diversity of the Particulate Fraction in the Surface Microlayer.

Blooms of Ostreopsis cf. ovata pose an emerging health threat, causing respiratory disorders in various coastal regions. This dinoflagellate produce potent phycotoxins named ovatoxins that can be transferred from the seawater to the atmosphere. However, the biotic and abiotic conditions affecting their transfer are still unknown. In this study, we investigate the sea-to-air transfer of O. cf ovata phycotoxins using a process study in an aerosol reference tank (MART) and field observations. The process study exhibited a positive correlation between the phycotoxin content in sea spray aerosol (up to 832.59 ng m-3) and the particulate phycotoxin fraction in the water column and surface microlayer. In contrast, in the natural system, aerosolized phycotoxins were only observed in one out of six air collection (total toxins 0.59 ng m-3) despite optimal wind conditions. In both the process study and the natural system, ovatoxins represented only a minor fraction of the total toxin content, which was comprised of up to 90% liguriatoxins. In seawater, while no solubilized ovatoxins were detected, the concentration in dissolved liguriatoxin-a reached up to 19.07 µg L-1. These results underscore the need for future research on the liguriatoxins, and on their toxicity to establish safe exposure thresholds for beachgoers.

Size-Dependent Nascent Sea Spray Aerosol Bounce Fractions and Estimated Viscosity: The Role of Divalent Cation Enrichment, Surface Tension, and the Kelvin Effect.

Viscosity, or the "thickness," of aerosols plays a key role in atmospheric processes like ice formation, water absorption, and heterogeneous kinetics. However, the viscosity of sea spray aerosols (SSA) has not been widely studied. This research explored the relationship between particle size and viscosity of authentic SSA particles through particle bounce, atomic force microscopy analysis, and predictive viscosity modeling from molecular composition. The study found that 40 nm SSA particles had estimated viscosities around 104 Pa·s and bounce fractions three times higher than 100 and 200 nm particles with less than 102 Pa·s at a relative humidity (RH) of 60%. Additional studies revealed the Kelvin effect and particle density, influenced by particle size, have a greater impact on size-dependent bounce fractions than changes in RH across impactor stages. While changes in the level of surfactants can impact particle bounce, the increased viscosity in smaller SSA is attributed to the formation of gel-like phase states caused by cation-organic cross-links between divalent calcium ions and organic anions enriched in the smaller particles. This work shows the smallest gel-like SSA particles observed in the field are highly viscous, which has implications for cloud formation, secondary aerosol growth, and pollutant transport in coastal environments.

Continuous measurements of volatile gases as detection of algae crop health.

Algae cultivation in open raceway ponds is considered the most economical method for photosynthetically producing biomass for biofuels, chemical feedstocks, and other high-value products. One of the primary challenges for open ponds is diminished biomass yields due to attack by grazers, competitors, and infectious organisms. Higher-frequency observations are needed for detection of grazer infections, which can rapidly reduce biomass levels. In this study, real-time measurements were performed using chemical ionization mass spectrometry (CIMS) to monitor the impact of grazer infections on cyanobacterial cultures. Numerous volatile gases were produced during healthy growth periods from freshwater Synechococcus elongatus Pasteur Culture Collection (PCC) 7942, with 6-methyl-5-hepten-2-one serving as a unique metabolic indicator of exponential growth. Following the introduction of a Tetrahymena ciliate grazer, the concentrations of multiple volatile species were observed to change after a latent period as short as 18 h. Nitrogenous gases, including ammonia and pyrroline, were found to be reliable indicators of grazing. Detection of grazing by CIMS showed indicators of infections much sooner than traditional methods, microscopy, and continuous fluorescence, which did not detect changes until 37 to 76 h after CIMS detection. CIMS analysis of gases produced by PCC 7942 further shows a complex temporal array of biomass-dependent volatile gas production, which demonstrates the potential for using volatile gas analysis as a diagnostic for grazer infections. Overall, these results show promise for the use of continuous volatile metabolite monitoring for the detection of grazing in algal monocultures, potentially reducing current grazing-induced biomass losses, which could save hundreds of millions of dollars.

Acidity across the interface from the ocean surface to sea spray aerosol.

Aerosols impact climate, human health, and the chemistry of the atmosphere, and aerosol pH plays a major role in the physicochemical properties of the aerosol. However, there remains uncertainty as to whether aerosols are acidic, neutral, or basic. In this research, we show that the pH of freshly emitted (nascent) sea spray aerosols is significantly lower than that of sea water (approximately four pH units, with pH being a log scale value) and that smaller aerosol particles below 1 µm in diameter have pH values that are even lower. These measurements of nascent sea spray aerosol pH, performed in a unique ocean-atmosphere facility, provide convincing data to show that acidification occurs "across the interface" within minutes, when aerosols formed from ocean surface waters become airborne. We also show there is a correlation between aerosol acidity and dissolved carbon dioxide but no correlation with marine biology within the seawater. We discuss the mechanisms and contributing factors to this acidity and its implications on atmospheric chemistry.

Bacterial and Chemical Evidence of Coastal Water Pollution from the Tijuana River in Sea Spray Aerosol.

Roughly half of the human population lives near the coast, and coastal water pollution (CWP) is widespread. Coastal waters along Tijuana, Mexico, and Imperial Beach (IB), USA, are frequently polluted by millions of gallons of untreated sewage and stormwater runoff. Entering coastal waters causes over 100 million global annual illnesses, but CWP has the potential to reach many more people on land via transfer in sea spray aerosol (SSA). Using 16S rRNA gene amplicon sequencing, we found sewage-associated bacteria in the polluted Tijuana River flowing into coastal waters and returning to land in marine aerosol. Tentative chemical identification from non-targeted tandem mass spectrometry identified anthropogenic compounds as chemical indicators of aerosolized CWP, but they were ubiquitous and present at highest concentrations in continental aerosol. Bacteria were better tracers of airborne CWP, and 40 tracer bacteria comprised up to 76% of the bacteria community in IB air. These findings confirm that CWP transfers in SSA and exposes many people along the coast. Climate change may exacerbate CWP with more extreme storms, and our findings call for minimizing CWP and investigating the health effects of airborne exposure.

Anthropogenic and Biogenic Contributions to the Organic Composition of Coastal Submicron Sea Spray Aerosol.

The organic composition of coastal sea spray aerosol is important for both atmospheric chemistry and public health but remains poorly characterized. Coastal waters contain an organic material derived from both anthropogenic processes, such as wastewater discharge, and biological processes, including biological blooms. Here, we probe the chemical composition of the organic fraction of sea spray aerosol over the course of the 2019 SeaSCAPE mesocosm experiment, in which a phytoplankton bloom was facilitated in natural coastal water from La Jolla, California. We apply untargeted two-dimensional gas chromatography to characterize submicron nascent sea spray aerosol samples, reporting ∼750 unique organic species traced over a 19 day phytoplankton bloom experiment. Categorization and quantitative compositional analysis reveal three major findings. First, anthropogenic species made up 30% of total submicron nascent sea spray aerosol organic mass under the pre-bloom condition. Second, biological activity drove large changes within the aerosolized carbon pool, decreasing the anthropogenic mass fraction by 89% and increasing the biogenic and biologically transformed fraction by a factor of 5.6. Third, biogenic marine organics are underrepresented in mass spectral databases in comparison to marine organic pollutants, with more than twice as much biogenic aerosol mass attributable to unlisted compounds.

Isotopic Insights into Organic Composition Differences between Supermicron and Submicron Sea Spray Aerosol.

To elucidate the seawater biological and physicochemical factors driving differences in organic composition between supermicron and submicron sea spray aerosol (SSAsuper and SSAsub), carbon isotopic composition (δ13C) measurements were performed on size-segregated, nascent SSA collected during a phytoplankton bloom mesocosm experiment. The δ13C measurements indicate that SSAsuper contains a mixture of particulate and dissolved organic material in the bulk seawater. After phytoplankton growth, a greater amount of freshly produced carbon was observed in SSAsuper with the proportional contribution being modulated by bacterial activity, emphasizing the importance of the microbial loop in controlling the organic composition of SSAsuper. Conversely, SSAsub exhibited no apparent relationship with biological activity but tracked closely with surface tension measurements probing the topmost ∼0.2-1.5 µm of the sea surface microlayer. This probing depth is similar to a bubble's film thickness at the ocean surface, suggesting that SSAsub organic composition may be influenced by the presence of surfactants at the air-sea interface that are transferred into SSAsub by bubble bursting. Our findings illustrate the substantial impact of seawater dynamics on the pronounced organic compositional differences between SSAsuper and SSAsub and demonstrate that these two SSA populations should be considered separately when assessing their contribution to marine aerosols and climate.

What were the historical reasons for the resistance to recognizing airborne transmission during the COVID-19 pandemic?

The question of whether SARS-CoV-2 is mainly transmitted by droplets or aerosols has been highly controversial. We sought to explain this controversy through a historical analysis of transmission research in other diseases. For most of human history, the dominant paradigm was that many diseases were carried by the air, often over long distances and in a phantasmagorical way. This miasmatic paradigm was challenged in the mid to late 19th century with the rise of germ theory, and as diseases such as cholera, puerperal fever, and malaria were found to actually transmit in other ways. Motivated by his views on the importance of contact/droplet infection, and the resistance he encountered from the remaining influence of miasma theory, prominent public health official Charles Chapin in 1910 helped initiate a successful paradigm shift, deeming airborne transmission most unlikely. This new paradigm became dominant. However, the lack of understanding of aerosols led to systematic errors in the interpretation of research evidence on transmission pathways. For the next five decades, airborne transmission was considered of negligible or minor importance for all major respiratory diseases, until a demonstration of airborne transmission of tuberculosis (which had been mistakenly thought to be transmitted by droplets) in 1962. The contact/droplet paradigm remained dominant, and only a few diseases were widely accepted as airborne before COVID-19: those that were clearly transmitted to people not in the same room. The acceleration of interdisciplinary research inspired by the COVID-19 pandemic has shown that airborne transmission is a major mode of transmission for this disease, and is likely to be significant for many respiratory infectious diseases.

CAICE Studies: Insights from a Decade of Ocean-Atmosphere Experiments in the Laboratory.

Ocean-atmosphere interactions control the composition of the atmosphere, hydrological cycle, and temperature of our planet and affect human and ecosystem health. Our understanding of the impact of ocean emissions on atmospheric chemistry and climate is limited relative to terrestrial systems, despite the fact that oceans cover the majority (71%) of the Earth. As a result, the impact of marine aerosols on clouds represents one of the largest uncertainties in our understanding of climate, which is limiting our ability to accurately predict the future temperatures of our planet. The emission of gases and particles from the ocean surface constitutes an important chemical link between the ocean and atmosphere and is mediated by marine biological, physical, and chemical processes. It is challenging to isolate the role of biological ocean processes on atmospheric chemistry in the real world, which contains a mixture of terrestrial and anthropogenic emissions. One decade ago, the NSF Center for Aerosol Impacts on Chemistry of the Environment (CAICE) took a unique ocean-in-the-laboratory approach to study the factors controlling the chemical composition of marine aerosols and their effects on clouds and climate. CAICE studies have demonstrated that the complex interplay of phytoplankton, bacteria, and viruses exerts significant control over sea spray aerosol composition and the production of volatile organic compounds. In addition, CAICE experiments have explored the physical production mechanisms and their impact on the properties of marine cloud condensation nuclei and ice nucleating particles, thus shedding light on connections between the oceans and cloud formation. As these ocean-in-the-laboratory experiments become more sophisticated, they allow for further exploration of the complexity of the processes that control atmospheric emissions from the ocean, as well as incorporating the effects of atmospheric aging and secondary oxidation processes. In the face of unprecedented global climate change, these results provide key insights into how our oceans and atmosphere are responding to human-induced changes to our planet.This Account presents results from a decade of research by chemists in the NSF Center for Aerosol Impacts on Chemistry of the Environment. The mission of CAICE involves taking a multidisciplinary approach to transform the ability to accurately predict the impact of marine aerosols on our environment by bringing the full real-world chemical complexity of the ocean and atmosphere into the laboratory. Toward this end, CAICE has successfully advanced the study of the ocean-atmosphere system under controlled laboratory settings through the stepwise simulation of physical production mechanisms and incorporation of marine microorganisms, building to systems that replicate real-world chemical complexity. This powerful approach has already made substantial progress in advancing our understanding of how ocean biology and physical processes affect the composition of nascent sea spray aerosol (SSA), as well as yielded insights that help explain longstanding discrepancies in field observations in the marine environment. CAICE research is now using laboratory studies to assess how real-world complexity, such as warming temperatures, ocean acidification, wind speed, biology, and anthropogenic perturbations, impacts the evolution of sea spray aerosol properties, as well as shapes the composition of the marine atmosphere.

Tandem Fluorescence Measurements of Organic Matter and Bacteria Released in Sea Spray Aerosols.

Biological aerosols, typically identified through their fluorescence properties, strongly influence clouds and climate. Sea spray aerosol (SSA) particles are a major source of biological aerosols, but detection in the atmosphere is challenging due to potential interference from other sources. Here, the fluorescence signature of isolated SSA, produced using laboratory-based aerosol generation methods, was analyzed and compared with two commonly used fluorescence techniques: excitation-emission matrix spectroscopy (EEMS) and the wideband integrated bioaerosol sensor (WIBS). A range of dynamic biological ocean scenarios were tested to compare EEMS and WIBS analyses of SSA. Both techniques revealed similar trends in SSA fluorescence intensity in response to changes in ocean microbiology, demonstrating the potential to use the WIBS to measure fluorescent aerosols alongside EEMS bulk solution measurements. Together, these instruments revealed a unique fluorescence signature of isolated, nascent SSA and, for the first time, a size-segregated emission of fluorescent species in SSA. Additionally, the fluorescence signature of aerosolized marine bacterial isolates was characterized and showed similar fluorescence peaks to those of SSA, suggesting that bacteria are a contributor to SSA fluorescence. Through investigation of isolated SSA, this study provides a reference for future identification of marine biological aerosols in a complex atmosphere.

Atmospheric Benzothiazoles in a Coastal Marine Environment.

Organic emissions from coastal waters play an important but poorly understood role in atmospheric chemistry in coastal regions. A mesocosm experiment focusing on facilitated biological blooms in coastal seawater, SeaSCAPE (Sea Spray Chemistry and Particle Evolution), was performed to study emission of volatile gases, primary sea spray aerosol, and formation of secondary marine aerosol as a function of ocean biological and chemical processes. Here, we report observations of aerosol-phase benzothiazoles in a marine atmospheric context with complementary measurements of dissolved-phase benzothiazoles. Though previously reported dissolved in polluted coastal waters, we report the first direct evidence of the transfer of these molecules from seawater into the atmosphere. We also report the first gas-phase observations of benzothiazole in the environment absent a direct industrial, urban, or rubber-based source. From the identities and temporal dynamics of the dissolved and aerosol species, we conclude that the presence of benzothiazoles in the coastal water (and thereby their emissions into the atmosphere) is primarily attributable to anthropogenic sources. Oxidation experiments to explore the atmospheric fate of gas-phase benzothiazole show that it produces secondary aerosol and gas-phase SO2, making it a potential contributor to secondary marine aerosol formation in coastal regions and a participant in atmospheric sulfur chemistry.

Liquid Sampling-Atmospheric Pressure Glow Discharge Ionization as a Technique for the Characterization of Salt-Containing Organic Samples.

Typical ionization techniques used for mass spectrometry (MS) analysis face challenges when trying to analyze organic species in a high-salt environment. Here, we present results using a recently developed ionization source, liquid sampling-atmospheric pressure glow discharge (LS-APGD), for marine-relevant salt-containing organic samples. Using two representative sample types, a triglyceride mixture and dissolved organic matter, this method is compared to traditional electrospray ionization (ESI) under saline and neat conditions. LS-APGD produced equal or higher (15%+) ion intensities than those of ESI for both salt-containing and neat samples, although important differences linked with adduct formation in high-salt conditions explain the molecular species observed. For all sample types, LS-APGD observed a higher diversity of molecules under optimized settings (0.25 mm electrode spacing at 20 mA) compared to traditional ESI. Furthermore, because the LS-APGD source ionizes molecular species in a ∼1 mm3 volume plasma using a low-power source, there is the potential for this method to be applied in field studies, eliminating desalting procedures, which can be time-consuming and nonideal for low-concentration species.

The role of jet and film drops in controlling the mixing state of submicron sea spray aerosol particles.

The oceans represent a significant global source of atmospheric aerosols. Sea spray aerosol (SSA) particles comprise sea salts and organic species in varying proportions. In addition to size, the overall composition of SSA particles determines how effectively they can form cloud droplets and ice crystals. Thus, understanding the factors controlling SSA composition is critical to predicting aerosol impacts on clouds and climate. It is often assumed that submicrometer SSAs are mainly formed by film drops produced from bursting bubble-cap films, which become enriched with hydrophobic organic species contained within the sea surface microlayer. In contrast, jet drops formed from the base of bursting bubbles are postulated to mainly produce larger supermicrometer particles from bulk seawater, which comprises largely salts and water-soluble organic species. However, here we demonstrate that jet drops produce up to 43% of total submicrometer SSA number concentrations, and that the fraction of SSA produced by jet drops can be modulated by marine biological activity. We show that the chemical composition, organic volume fraction, and ice nucleating ability of submicrometer particles from jet drops differ from those formed from film drops. Thus, the chemical composition of a substantial fraction of submicrometer particles will not be controlled by the composition of the sea surface microlayer, a major assumption in previous studies. This finding has significant ramifications for understanding the factors controlling the mixing state of submicrometer SSA particles and must be taken into consideration when predicting SSA impacts on clouds and climate.

Improving our fundamental understanding of the role of aerosol-cloud interactions in the climate system.

The effect of an increase in atmospheric aerosol concentrations on the distribution and radiative properties of Earth's clouds is the most uncertain component of the overall global radiative forcing from preindustrial time. General circulation models (GCMs) are the tool for predicting future climate, but the treatment of aerosols, clouds, and aerosol-cloud radiative effects carries large uncertainties that directly affect GCM predictions, such as climate sensitivity. Predictions are hampered by the large range of scales of interaction between various components that need to be captured. Observation systems (remote sensing, in situ) are increasingly being used to constrain predictions, but significant challenges exist, to some extent because of the large range of scales and the fact that the various measuring systems tend to address different scales. Fine-scale models represent clouds, aerosols, and aerosol-cloud interactions with high fidelity but do not include interactions with the larger scale and are therefore limited from a climatic point of view. We suggest strategies for improving estimates of aerosol-cloud relationships in climate models, for new remote sensing and in situ measurements, and for quantifying and reducing model uncertainty.

Sea spray aerosol as a unique source of ice nucleating particles.

Ice nucleating particles (INPs) are vital for ice initiation in, and precipitation from, mixed-phase clouds. A source of INPs from oceans within sea spray aerosol (SSA) emissions has been suggested in previous studies but remained unconfirmed. Here, we show that INPs are emitted using real wave breaking in a laboratory flume to produce SSA. The number concentrations of INPs from laboratory-generated SSA, when normalized to typical total aerosol number concentrations in the marine boundary layer, agree well with measurements from diverse regions over the oceans. Data in the present study are also in accord with previously published INP measurements made over remote ocean regions. INP number concentrations active within liquid water droplets increase exponentially in number with a decrease in temperature below 0 °C, averaging an order of magnitude increase per 5 °C interval. The plausibility of a strong increase in SSA INP emissions in association with phytoplankton blooms is also shown in laboratory simulations. Nevertheless, INP number concentrations, or active site densities approximated using "dry" geometric SSA surface areas, are a few orders of magnitude lower than corresponding concentrations or site densities in the surface boundary layer over continental regions. These findings have important implications for cloud radiative forcing and precipitation within low-level and midlevel marine clouds unaffected by continental INP sources, such as may occur over the Southern Ocean.

Sea Spray Aerosol: The Chemical Link between the Oceans, Atmosphere, and Climate.

The oceans, atmosphere, and clouds are all interconnected through the release and deposition of chemical species, which provide critical feedback in controlling the composition of our atmosphere and climate. To better understand the couplings between the ocean and atmosphere, it is critical to improve our understanding of the processes that control sea spray aerosol (SSA) composition and which ones plays the dominate role in regulating atmospheric chemistry and climate.