Abstract

Ocean waves transfer sea spray aerosol (SSA) to the atmosphere, and these SSA particles can be enriched in organic matter relative to salts compared to seawater ratios. A fundamental understanding of the factors controlling the transfer of biogenic organic matter from the ocean to the atmosphere remains elusive. Field studies that focus on understanding the connection between organic species in seawater and SSA are complicated by the numerous processes and sources affecting the composition of aerosols in the marine environment. Here, an isolated ocean–atmosphere system enables direct measurements of the sea–air transfer of different classes of biogenic organic matter over the course of two phytoplankton blooms. By measuring excitation–emission matrices of bulk seawater, the sea surface microlayer, and SSA, we investigate time series of the transfer of fluorescent species including chlorophyll-a, protein-like substances, and humic-like substances. Herein, we show the emergence of different molecular classes in SSA at specific times over the course of a phytoplankton bloom, suggesting that SSA chemical composition changes over time in response to changing ocean biological conditions. We compare the temporal behaviors for the transfer of each component, and discuss the factors contributing to differences in transfer between phases.

Highlights

  • Ocean waves transfer sea spray aerosol (SSA) to the atmosphere, and these SSA particles can be enriched in organic matter relative to salts compared to seawater ratios

  • The two microcosm experiments were conducted in the Marine Aerosol Reference Tank (MART) and are referred to as MART A and MART B

  • Seawater used in the MART A and MART B microcosm experiments had different initial chlorophyll-a levels (1.33 mg/m3 for MART A; 4.49 mg/m3 for MART B), and the same nutrient amounts were added to both MARTs to induce phytoplankton blooms

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Summary

Introduction

Ocean waves transfer sea spray aerosol (SSA) to the atmosphere, and these SSA particles can be enriched in organic matter relative to salts compared to seawater ratios. We investigate the physical and chemical mechanisms controlling the sea–air transfer of organic species in SSA by probing the composition of collected bulk seawater, SSML, and SSA samples with excitation-emission matrix (EEM) spectroscopy in combination with parallel factor analysis (PARAFAC)[29–31]. We describe how the fluorescence signals of chlorophyll-a, protein-like substances, and HULIS changed over the course of the phytoplankton bloom and discuss how these changes are associated with different factors influencing sea–air transfer.

Results
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