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2.
Environ Sci Technol ; 55(8): 5171-5179, 2021 04 20.
Artigo em Inglês | MEDLINE | ID: mdl-33755426

RESUMO

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.


Assuntos
Bactérias , Água do Mar , Aerossóis , Atmosfera , Análise Espectral
4.
Chemosphere ; 271: 129450, 2021 May.
Artigo em Inglês | MEDLINE | ID: mdl-33460888

RESUMO

Urbanization along coastlines alters marine ecosystems including contributing molecules of anthropogenic origin to the coastal dissolved organic matter (DOM) pool. A broad assessment of the nature and extent of anthropogenic impacts on coastal ecosystems is urgently needed to inform regulatory guidelines and ecosystem management. Recently, non-targeted tandem mass spectrometry approaches are gaining momentum for the analysis of global organic matter composition (chemotypes) including a wide array of natural and anthropogenic compounds. In line with these efforts, we developed a non-targeted liquid chromatography tandem mass spectrometry (LC-MS/MS) workflow that utilizes advanced data analysis approaches such as feature-based molecular networking and repository-scale spectrum searches. This workflow allows the scalable comparison and mapping of seawater chemotypes from large-scale spatial surveys as well as molecular family level annotation of unknown compounds. As a case study, we visualized organic matter chemotype shifts in coastal environments in northern San Diego, USA, after notable rain fall in winter 2017/2018 and highlight potential anthropogenic impacts. The observed seawater chemotype, consisting of 4384 LC-MS/MS features, shifted significantly after a major rain event. Molecular drivers of this shift could be attributed to multiple anthropogenic compounds, including pesticides (Imazapyr and Isoxaben), cleaning products (Benzyl-tetradecyl-dimethylammonium) and chemical additives (Hexa (methoxymethyl)melamine) and potential degradation products. By expanding the search of identified xenobiotics to other public tandem mass spectrometry datasets, we further contextualized their possible origin and show their importance in other ecosystems. The mass spectrometry and data analysis pipelines applied here offer a scalable framework for future molecular mapping and monitoring of marine ecosystems, which will contribute to a deliberate assessment of how chemical pollution impacts our oceans.


Assuntos
Ecossistema , Espectrometria de Massas em Tandem , Cromatografia Líquida , Oceanos e Mares , Água do Mar
5.
Proc Natl Acad Sci U S A ; 118(2)2021 01 12.
Artigo em Inglês | MEDLINE | ID: mdl-33376210

RESUMO

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.

6.
Science ; 370(6521): 1170, 2020 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-33273091
9.
Acc Chem Res ; 53(11): 2510-2520, 2020 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-33086794

RESUMO

ConspectusOcean-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.

11.
Anal Chem ; 92(13): 8845-8851, 2020 07 07.
Artigo em Inglês | MEDLINE | ID: mdl-32441094

RESUMO

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.

13.
Environ Sci Process Impacts ; 20(11): 1559-1569, 2018 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-30382263

RESUMO

Heterogeneous ice nucleation in the atmosphere regulates cloud properties, such as phase (ice versus liquid) and lifetime. Aerosol particles of marine origin are relevant ice nucleating particle sources when marine aerosol layers are lifted over mountainous terrain and in higher latitude ocean boundary layers, distant from terrestrial aerosol sources. Among many particle compositions associated with ice nucleation by sea spray aerosols are highly saturated fatty acids. Previous studies have not demonstrated their ability to freeze dilute water droplets. This study investigates ice nucleation by monolayers at the surface of supercooled droplets and as crystalline particles at temperatures exceeding the threshold for homogeneous freezing. Results show the poor efficiency of long chain fatty acid (C16, C18) monolayers in templating freezing of pure water droplets and seawater subphase to temperatures of at least -30 °C, consistent with theory. This contrasts with freezing of fatty alcohols (C22 used here) at nearly 20 °C warmer. Evaporation of µL-sized droplets to promote structural compression of a C19 acid monolayer did not favor warmer ice formation of drops. Heterogeneous ice nucleation occurred for nL-sized droplets condensed on 5 to 100 µm crystalline particles of fatty acid (C12 to C20) at a range of temperatures below -28 °C. These experiments suggest that fatty acids nucleate ice at warmer than -36 °C only when the crystalline phase is present. Rough estimates of ice active site densities are consistent with those of marine aerosols, but require knowledge of the proportion of surface area comprised of fatty acids for application.


Assuntos
Aerossóis/química , Atmosfera/química , Ácidos Graxos/química , Gelo , Água do Mar/química , Ácidos Graxos/análise , Congelamento , Transição de Fase , Análise Espectral/métodos , Temperatura , Água/química
14.
Nat Commun ; 9(1): 2017, 2018 05 22.
Artigo em Inglês | MEDLINE | ID: mdl-29789621

RESUMO

Ocean-derived, airborne microbes play important roles in Earth's climate system and human health, yet little is known about factors controlling their transfer from the ocean to the atmosphere. Here, we study microbiomes of isolated sea spray aerosol (SSA) collected in a unique ocean-atmosphere facility and demonstrate taxon-specific aerosolization of bacteria and viruses. These trends are conserved within taxonomic orders and classes, and temporal variation in aerosolization is similarly shared by related taxa. We observe enhanced transfer into SSA of Actinobacteria, certain Gammaproteobacteria, and lipid-enveloped viruses; conversely, Flavobacteriia, some Alphaproteobacteria, and Caudovirales are generally under-represented in SSA. Viruses do not transfer to SSA as efficiently as bacteria. The enrichment of mycolic acid-coated Corynebacteriales and lipid-enveloped viruses (inferred from genomic comparisons) suggests that hydrophobic properties increase transport to the sea surface and SSA. Our results identify taxa relevant to atmospheric processes and a framework to further elucidate aerosolization mechanisms influencing microbial and viral transport pathways.


Assuntos
Bactérias/genética , DNA Bacteriano/genética , DNA Viral/genética , Filogenia , Fitoplâncton/genética , Vírus/genética , Aerossóis , Atmosfera , Bactérias/química , Bactérias/classificação , Código de Barras de DNA Taxonômico , Ecossistema , Interações Hidrofóbicas e Hidrofílicas , Fitoplâncton/química , Fitoplâncton/classificação , Água do Mar/microbiologia , Água do Mar/virologia , Vírus/química , Vírus/classificação , Volatilização
15.
ACS Cent Sci ; 4(12): 1617-1623, 2018 Dec 26.
Artigo em Inglês | MEDLINE | ID: mdl-30648145

RESUMO

Atmospheric aerosols have long been known to alter climate by scattering incoming solar radiation and acting as seeds for cloud formation. These processes have vast implications for controlling the chemistry of our environment and the Earth's climate. Sea spray aerosol (SSA) is emitted over nearly three-quarters of our planet, yet precisely how SSA impacts Earth's radiation budget remains highly uncertain. Over the past several decades, studies have shown that SSA particles are far more complex than just sea salt. Ocean biological and physical processes produce individual SSA particles containing a diverse array of biological species including proteins, enzymes, bacteria, and viruses and a diverse array of organic compounds including fatty acids and sugars. Thus, a new frontier of research is emerging at the nexus of chemistry, biology, and atmospheric science. In this Outlook article, we discuss how current and future aerosol chemistry research demands a tight coupling between experimental (observational and laboratory studies) and computational (simulation-based) methods. This integration of approaches will enable the systematic interrogation of the complexity within individual SSA particles at a level that will enable prediction of the physicochemical properties of real-world SSA, ultimately illuminating the detailed mechanisms of how the constituents within individual SSA impact climate.

16.
Acc Chem Res ; 50(3): 599-604, 2017 03 21.
Artigo em Inglês | MEDLINE | ID: mdl-28945390

RESUMO

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.

17.
Anal Chem ; 89(19): 10162-10170, 2017 10 03.
Artigo em Inglês | MEDLINE | ID: mdl-28846845

RESUMO

Ocean-derived microbes in sea spray aersosol (SSA) have the potential to influence climate and weather by acting as ice nucleating particles in clouds. Single particle mass spectrometers (SPMSs), which generate in situ single particle composition data, are excellent tools for characterizing aerosols under changing environmental conditions as they can provide high temporal resolution and require no sample preparation. While SPMSs have proven capable of detecting microbes, these instruments have never been utilized to definitively identify aerosolized microbes in ambient sea spray aersosol. In this study, an aerosol time-of-flight mass spectrometer was used to analyze laboratory generated SSA produced from natural seawater in a marine aerosol reference tank. We present the first description of a population of biological SSA mass spectra (BioSS), which closely match the ion signatures observed in previous terrestrial microbe studies. The fraction of BioSS dramatically increased in the largest supermicron particles, consistent with field and laboratory measurements of microbes ejected by bubble bursting, further supporting the assignment of BioSS mass spectra as microbes. Finally, as supported by analysis of inorganic ion signals, we propose that dry BioSS particles have heterogeneous structures, with microbes adhered to sodium chloride nodules surrounded by magnesium-enriched coatings. Consistent with this structure, chlorine-containing ion markers were ubiquitous in BioSS spectra and identified as possible tracers for distinguishing recently aerosolized marine from terrestrial microbes.


Assuntos
Aerossóis/análise , Espectrometria de Massas , Água do Mar/microbiologia , Aerossóis/química , Bactérias/química , Bactérias/metabolismo , Eucariotos/química , Eucariotos/metabolismo , Magnésio/química , Tamanho da Partícula , Fitoplâncton/química , Fitoplâncton/metabolismo , Cloreto de Sódio/química , Vírus/química , Vírus/metabolismo
18.
Proc Natl Acad Sci U S A ; 114(27): 6978-6983, 2017 07 03.
Artigo em Inglês | MEDLINE | ID: mdl-28630346

RESUMO

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.

19.
Environ Sci Technol ; 51(7): 3660-3668, 2017 04 04.
Artigo em Inglês | MEDLINE | ID: mdl-28299935

RESUMO

Knowledge of the surface composition of sea spray aerosols (SSA) is critical for understanding and predicting climate-relevant impacts. Offline microscopy and spectroscopy studies have shown that dry supermicron SSA tend to be spatially heterogeneous particles with sodium- and chloride-rich cores surrounded by organic enriched surface layers containing minor inorganic seawater components such as magnesium and calcium. At the same time, single-particle mass spectrometry reveals several different mass spectral ion patterns, suggesting that there may be a number of chemically distinct particle types. This study investigates factors controlling single particle mass spectra of nascent supermicron SSA. Depth profiling experiments conducted on SSA generated by a fritted bubbler and total ion intensity analysis of SSA generated by a marine aerosol reference tank were compared with observations of ambient SSA observed at two coastal locations. Analysis of SSA produced by utilizing controlled laboratory methods reveals that single-particle mass spectra with weak sodium ion signals can be produced by the desorption of the surface of typical dry SSA particles composed of salt cores and organic-rich coatings. Thus, this lab-based study for the first time unifies findings from offline and online measurements as well as lab and field studies of the SSA particle-mixing state.


Assuntos
Aerossóis , Espectrometria de Massas , Tamanho da Partícula , Água do Mar/química , Cloreto de Sódio/química , Análise Espectral
20.
Environ Sci Technol ; 51(3): 1348-1356, 2017 02 07.
Artigo em Inglês | MEDLINE | ID: mdl-28005339

RESUMO

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.


Assuntos
Aerossóis , Poeira , Clima , Sais , Molhabilidade
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