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To test the hypothesis that an abiotic Earth and its inert atmosphere could form chemically reactive carbon-and nitrogen-containing compounds, we designed a plasma electrochemical setup to mimic lightning-induced electrochemistry under steady-state conditions of the early Earth. Air-gap electrochemical reactions at air-water-ground interfaces lead to remarkable yields, with up to 40 moles of carbon dioxide being reduced into carbon monoxide and formic acid, and 3 moles of gaseous nitrogen being fixed into nitrate, nitrite, and ammonium ions, per mole of transmitted electrons. Interfaces enable reactants (e.g., minerals) that may have been on land, in lakes, and in oceans to participate in radical and redox reactions, leading to higher yields compared to gas-phase-only reactions. Cloud-to-ground lightning strikes could have generated high concentrations of reactive molecules locally, establishing diverse feedstocks for early life to emerge and survive globally. [ABSTRACT FROM AUTHOR]

Studies over the last two decades have shown that submicron particulates (SMPs) can be transferred from the seawater into sea spray aerosol (SSA), potentially impacting SSA cloud seeding ability. This work reports the first concurrent bulk and sea surface microlayer (SSML) SMP (0.4–1.0 μm) measurements, made during two mesocosm phytoplankton blooms in a region devoid of active wave breaking and bubble formation, providing insight into how biological and physicochemical processes influence seawater SMP distributions. Modal analyses of the SMP size distributions revealed contributions from multiple, biologically related particulate populations that were controlled by the microbial loop. With negligible bubble scavenging occurring, SSML enrichment of SMPs remained low throughout both experiments, suggesting scavenging is vital for SMP enrichment in the SSML. Our findings are discussed in the context of SMP transfer into SSA and its potential importance for SSA cloud seeding ability. Plain Language Summary: Research has shown that particulates can be transferred from the ocean into sea spray aerosol (SSA) when bubbles burst at the ocean surface. This transfer is important because incorporation of seawater particulates into SSA can impact its ability to seed water and ice clouds. During the Sea Spray Chemistry and Particulate Evolution (SeaSCAPE) study, submicron particulates (SMPs, 0.4–1.0 μm) were measured daily in the sea surface microlayer (SSML), the topmost 1–1,000 μm of the ocean surface, and the underlying bulk seawater over the course of two phytoplankton growth experiments. The objective of this study was to assess the influence of biological activity on SMP concentrations and distributions in the seawater. Our results indicate that biological growth led to increased SMP production, and the size distribution of SMPs produced was dependent on the phase of the bloom growth. Additionally, almost no SSML enrichment of SMPs occurred without active wave breaking and bubble formation, highlighting the significance of biological activity and bubble scavenging/bursting for particulate transfer into SSA. These findings are discussed in the context of potential SMP impacts on SSA cloud forming ability. Key Points: The concentration of 0.4–1.0 μm seawater particulates is higher during a phytoplankton bloomThe biologically induced increase in seawater submicron particulates is size dependent and influenced by the phase of the bloomParticulate enrichment in the sea surface microlayer is low in the absence of wave breaking and bubble scavenging [ABSTRACT FROM AUTHOR]

The oxidation of dimethyl sulfide (DMS; CH 3 SCH 3), emitted from the surface ocean, contributes to the formation of Aitken mode particles and their growth to cloud condensation nuclei (CCN) sizes in remote marine environments. It is not clear whether other less commonly measured marine-derived, sulfur-containing gases share similar dynamics to DMS and contribute to secondary marine aerosol formation. Here, we present measurements of gas-phase volatile organosulfur molecules taken with a Vocus proton-transfer-reaction high-resolution time-of-flight mass spectrometer during a mesocosm phytoplankton bloom experiment using coastal seawater. We show that DMS, methanethiol (MeSH; CH 3 SH), and benzothiazole (C 7 H 5 NS) account for on average over 90 % of total gas-phase sulfur emissions, with non-DMS sulfur sources representing 36.8 ± 7.7 % of sulfur emissions during the first 9 d of the experiment in the pre-bloom phase prior to major biological growth, before declining to 14.5 ± 6.0 % in the latter half of the experiment when DMS dominates during the bloom and decay phases. The molar ratio of DMS to MeSH during the pre-bloom phase (DMS : MeSH = 4.60 ± 0.93) was consistent with the range of previously calculated ambient DMS-to-MeSH sea-to-air flux ratios. As the experiment progressed, the DMS to MeSH emission ratio increased significantly, reaching 31.8 ± 18.7 during the bloom and decay. Measurements of dimethylsulfoniopropionate (DMSP), heterotrophic bacteria, and enzyme activity in the seawater suggest the DMS : MeSH ratio is a sensitive indicator of the bacterial sulfur demand and the composition and magnitude of available sulfur sources in seawater. The evolving DMS : MeSH ratio and the emission of a new aerosol precursor gas, benzothiazole, have important implications for secondary sulfate formation pathways in coastal marine environments. [ABSTRACT FROM AUTHOR]

The oxidation of dimethyl sulfide (DMS; CH3SCH3), emitted from the surface ocean, contributes to the formation of Aitken mode particles and their growth to cloud condensation nuclei (CCN) sizes in remote marine environments. It is not clear whether other, less commonly measured marine-derived, sulfur-containing gases share similar dynamics to DMS and contribute to secondary marine aerosol formation. Here, we present measurements of gas-phase volatile organosulfur molecules taken with a Vocus proton transfer reaction high resolution time-of-flight mass spectrometer during a mesocosm phytoplankton bloom experiment using coastal seawater. We show that DMS, methanethiol (MeSH; CH3SH), and benzothiazole (C7H5NS) account for on average over 90% of total gas-phase sulfur emissions, with non-DMS sulfur sources representing 36.8 ± 7.7% of sulfur emissions during the first nine days of the experiment in the pre-bloom phase prior to major biological growth, before declining to 14.5 ± 6.0% in the latter half of the experiment when DMS dominates during the bloom and decay phases. The molar ratio of DMS to MeSH during the pre-bloom phase (DMS:MeSH = 4.60 ± 0.93) was consistent with the range of previously calculated ambient DMS to MeSH sea-to-air flux ratios. As the experiment progressed, the DMS to MeSH emission ratio increased significantly, reaching 31.8 ± 18.7 during the bloom and decay. Measurements of dimethylsulfoniopropionate (DMSP), heterotrophic bacteria, and enzyme activity in the seawater suggest the DMS:MeSH ratio is a sensitive indicator of the bacterial sulfur demand and the composition and magnitude of available sulfur sources in seawater. The evolving DMS:MeSH ratio and the emission of a new aerosol precursor gas, benzothiazole, have important implications for secondary sulfate formation pathways in coastal marine environments. [ABSTRACT FROM AUTHOR]

To test the hypothesis that an abiotic Earth and its inert atmosphere could form chemically reactive carbon- and nitrogen-containing compounds, we designed a plasma electrochemical setup to mimic lightning-induced electrochemistry under steady-state conditions of the early Earth. Air-gap electrochemical reactions at air-water-ground interfaces lead to remarkable yields, with up to 40 moles of carbon dioxide being reduced into carbon monoxide and formic acid, and 3 moles of gaseous nitrogen being fixed into nitrate, nitrite, and ammonium ions, per mole of transmitted electrons. Interfaces enable reactants (e.g., minerals) that may have been on land, in lakes, and in oceans to participate in radical and redox reactions, leading to higher yields compared to gas-phase-only reactions. Cloud-to-ground lightning strikes could have generated high concentrations of reactive molecules locally, establishing diverse feedstocks for early life to emerge and survive globally., Competing Interests: Competing interests statement:Harvard University has filed patent applications PCT/US2023/077332 and PCT/US2024/017763.