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.

The Sea Spray Chemistry and Particle Evolution study (SeaSCAPE): overview and experimental methods.

Marine aerosols strongly influence climate through their interactions with solar radiation and clouds. However, significant questions remain regarding the influences of biological activity and seawater chemistry on the flux, chemical composition, and climate-relevant properties of marine aerosols and gases. Wave channels, a traditional tool of physical oceanography, have been adapted for large-scale ocean-atmosphere mesocosm experiments in the laboratory. These experiments enable the study of aerosols under controlled conditions which isolate the marine system from atmospheric anthropogenic and terrestrial influences. Here, we present an overview of the 2019 Sea Spray Chemistry and Particle Evolution (SeaSCAPE) study, which was conducted in an 11 800 L wave channel which was modified to facilitate atmospheric measurements. The SeaSCAPE campaign sought to determine the influence of biological activity in seawater on the production of primary sea spray aerosols, volatile organic compounds (VOCs), and secondary marine aerosols. Notably, the SeaSCAPE experiment also focused on understanding how photooxidative aging processes transform the composition of marine aerosols. In addition to a broad range of aerosol, gas, and seawater measurements, we present key results which highlight the experimental capabilities during the campaign, including the phytoplankton bloom dynamics, VOC production, and the effects of photochemical aging on aerosol production, morphology, and chemical composition. Additionally, we discuss the modifications made to the wave channel to improve aerosol production and reduce background contamination, as well as subsequent characterization experiments. The SeaSCAPE experiment provides unique insight into the connections between marine biology, atmospheric chemistry, and climate-relevant aerosol properties, and demonstrates how an ocean-atmosphere-interaction facility can be used to isolate and study reactions in the marine atmosphere in the laboratory under more controlled conditions.

Airborne transmission pathway for coastal water pollution.

Each year, over one hundred million people become ill and tens of thousands die from exposure to viruses and bacteria from sewage transported to the ocean by rivers, estuaries, stormwater, and other coastal discharges. Water activities and seafood consumption have been emphasized as the major exposure pathways to coastal water pollution. In contrast, relatively little is known about the potential for airborne exposure to pollutants and pathogens from contaminated seawater. The Cross Surfzone/Inner-shelf Dye Exchange (CSIDE) study was a large-scale experiment designed to investigate the transport pathways of water pollution along the coast by releasing dye into the surfzone in Imperial Beach, CA. Additionally, we leveraged this ocean-focused study to investigate potential airborne transmission of coastal water pollution by collecting complementary air samples along the coast and inland. Aerial measurements tracked sea surface dye concentrations along 5+ km of coast at 2 m × 2 m resolution. Dye was detected in the air over land for the first 2 days during two of the three dye releases, as far as 668 m inland and 720 m downwind of the ocean. These coordinated water/air measurements, comparing dye concentrations in the air and upwind source waters, provide insights into the factors that lead to the water-to-air transfer of pollutants. These findings show that coastal water pollution can reach people through an airborne pathway and this needs to be taken into account when assessing the full impact of coastal ocean pollution on public health. This study sets the stage for further studies to determine the details and importance of airborne exposure to sewage-based pathogens and toxins in order to fully assess the impact of coastal pollution on public health.

Ion identity molecular networking for mass spectrometry-based metabolomics in the GNPS environment.

Molecular networking connects mass spectra of molecules based on the similarity of their fragmentation patterns. However, during ionization, molecules commonly form multiple ion species with different fragmentation behavior. As a result, the fragmentation spectra of these ion species often remain unconnected in tandem mass spectrometry-based molecular networks, leading to redundant and disconnected sub-networks of the same compound classes. To overcome this bottleneck, we develop Ion Identity Molecular Networking (IIMN) that integrates chromatographic peak shape correlation analysis into molecular networks to connect and collapse different ion species of the same molecule. The new feature relationships improve network connectivity for structurally related molecules, can be used to reveal unknown ion-ligand complexes, enhance annotation within molecular networks, and facilitate the expansion of spectral reference libraries. IIMN is integrated into various open source feature finding tools and the GNPS environment. Moreover, IIMN-based spectral libraries with a broad coverage of ion species are publicly available.

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.

Enrichment of Saccharides and Divalent Cations in Sea Spray Aerosol During Two Phytoplankton Blooms.

Sea spray aerosol (SSA) is a globally important source of particulate matter. A mesocosm study was performed to determine the relative enrichment of saccharides and inorganic ions in nascent fine (PM2.5) and coarse (PM10-2.5) SSA and the sea surface microlayer (SSML) relative to bulk seawater. Saccharides comprise a significant fraction of organic matter in fine and coarse SSA (11 and 27%, respectively). Relative to sodium, individual saccharides were enriched 14-1314-fold in fine SSA, 3-138-fold in coarse SSA, but only up to 1.0-16.2-fold in SSML. Enrichments in SSML were attributed to rising bubbles that scavenge surface-active species from seawater, while further enrichment in fine SSA likely derives from bubble films. Mean enrichment factors for major ions demonstrated significant enrichment in fine SSA for potassium (1.3), magnesium (1.4), and calcium (1.7), likely because of their interactions with organic matter. Consequently, fine SSA develops a salt profile significantly different from that of seawater. Maximal enrichments of saccharides and ions coincided with the second of two phytoplankton blooms, signifying the influence of ocean biology on selective mass transfer across the ocean-air interface.

Microbial Control of Sea Spray Aerosol Composition: A Tale of Two Blooms.

With the oceans covering 71% of the Earth, sea spray aerosol (SSA) particles profoundly impact climate through their ability to scatter solar radiation and serve as seeds for cloud formation. The climate properties can change when sea salt particles become mixed with insoluble organic material formed in ocean regions with phytoplankton blooms. Currently, the extent to which SSA chemical composition and climate properties are altered by biological processes in the ocean is uncertain. To better understand the factors controlling SSA composition, we carried out a mesocosm study in an isolated ocean-atmosphere facility containing 3,400 gallons of natural seawater. Over the course of the study, two successive phytoplankton blooms resulted in SSA with vastly different composition and properties. During the first bloom, aliphatic-rich organics were enhanced in submicron SSA and tracked the abundance of phytoplankton as indicated by chlorophyll-a concentrations. In contrast, the second bloom showed no enhancement of organic species in submicron particles. A concurrent increase in ice nucleating SSA particles was also observed only during the first bloom. Analysis of the temporal variability in the concentration of aliphatic-rich organic species, using a kinetic model, suggests that the observed enhancement in SSA organic content is set by a delicate balance between the rate of phytoplankton primary production of labile lipids and enzymatic induced degradation. This study establishes a mechanistic framework indicating that biological processes in the ocean and SSA chemical composition are coupled not simply by ocean chlorophyll-a concentrations, but are modulated by microbial degradation processes. This work provides unique insight into the biological, chemical, and physical processes that control SSA chemical composition, that when properly accounted for may explain the observed differences in SSA composition between field studies.

Blank corrections for ramped pyrolysis radiocarbon dating of sedimentary and soil organic carbon.

Ramped pyrolysis (RP) targets distinct components of soil and sedimentary organic carbon based on their thermochemical stabilities and allows the determination of the full spectrum of radiocarbon ((14)C) ages present in a soil or sediment sample. Extending the method into realms where more precise ages are needed or where smaller samples need to be measured involves better understanding of the blank contamination associated with the method. Here, we use a compiled data set of RP measurements of samples of known age to evaluate the mass of the carbon blank and its associated (14)C signature, and to assess the performance of the RP system. We estimate blank contamination during RP using two methods, the modern-dead and the isotope dilution method. Our results indicate that during one complete RP run samples are contaminated by 8.8 ± 4.4 µg (time-dependent) of modern carbon (MC, fM ∼ 1) and 4.1 ± 5.5 µg (time-independent) of dead carbon (DC, fM ∼ 0). We find that the modern-dead method provides more accurate estimates of uncertainties in blank contamination; therefore, the isotope dilution method should be used with caution when the variability of the blank is high. Additionally, we show that RP can routinely produce accurate (14)C dates with precisions ∼100 (14)C years for materials deposited in the last 10,000 years and ∼300 (14)C years for carbon with (14)C ages of up to 20,000 years.

Varying relative degradation rates of oil in different forms and environments revealed by ramped pyrolysis.

Degradation of oil contamination yields stabilized products by removing and transforming reactive and volatile compounds. In contaminated coastal environments, the processes of degradation are influenced by shoreline energy, which increases the surface area of the oil as well as exchange between oil, water, sediments, microbes, oxygen, and nutrients. Here, a ramped pyrolysis carbon isotope technique is employed to investigate thermochemical and isotopic changes in organic material from coastal environments contaminated with oil from the 2010 BP Deepwater Horizon oil spill. Oiled beach sediment, tar ball, and marsh samples were collected from a barrier island and a brackish marsh in southeast Louisiana over a period of 881 days. Stable carbon ((13)C) and radiocarbon ((14)C) isotopic data demonstrate a predominance of oil-derived carbon in the organic material. Ramped pyrolysis profiles indicate that the organic material was transformed into more stable forms. Our data indicate relative rates of stabilization in the following order, from fastest to slowest: high energy beach sediments > low energy beach sediments > marsh > tar balls. Oil was transformed most rapidly where shoreline energy and the rates of oil dispersion and exchange with water, sediments, microbes, oxygen, and nutrients were greatest. Still, isotope data reveal persistence of oil.