Harmful algal blooms (HABs) in lakes and estuaries, caused by cyanobacteria, pose various threats to humans and the environment. Cyanobacteria produce microcystins (MCs) that make animals and people sick. Once airborne, cyanobacterial aerosols are rapidly transformed through heterogeneous reactions with atmospheric oxidants, which tend to occur much faster in air than in water. The important aspects of these transformations include the degradation of MCs and the production of reactive oxygen species (ROS) from oxidized organic matter (OM) in cyanobacterial aerosol. In this study, MCs in aerosols and water samples, collected in lakes (Lake Okeechobee, Georges Lake, and Doctors Lake) of Florida during HABs, were measured using enzyme-linked immunosorbent assay kits. Organic hydroperoxides (OHP) and the oxidative potential (OP) associated with aerosols collected at Doctors Lake were measured with 4-nitrophenylboronic acid and dithiothreitol assays, respectively. The decay of MCs and the evolution of ROS in cyanobacterial aerosols were also demonstrated in an outdoor chamber under ambient sunlight. MC concentrations (0.4–2.1 μg/L) during HAB periods were higher than the US EPA guideline (0.3 μg/L for pre-school age and 1.6 μg/L for school-age and above). Airborne MC concentrations ranged from 0.2 to 5.7 ng/m3. Regulations for airborne MC concentrations are yet to be established. In both field and chamber data, MCs decomposed but ROS substantially increased as aerosols atmospherically oxidized. Aerosolized OM concentrations during HABs were higher than those in dormant periods. OM in cyanobacterial aerosols was enriched at estuary Doctors Lake with high inorganic salt concentrations due to salting-out of water-soluble organics into lake-surface layers. Aerosolized OM concentrations were positively corelated to OP and OHP (r = 0.96 and 0.85, respectively) at Doctors Lake suggesting that cyanobacterial aerosols might adversely influence respiratory health. The longitudinal health impacts of aerosolized cyanobacteria emitted from HABs should be investigated in the future.
more »
« less
This content will become publicly available on February 1, 2026
Enrichment of lipophilic brevetoxins in sea spray aerosol during red-tides
Abstract Red tide is caused by the accumulation of Karenia (K.) brevis, which produces brevetoxin (BTx), a neurotoxin. Excreted BTx is incorporated into sea spray aerosol (SSA), which is created from the bursting of bubbles at the ocean’s surface. For the first time, this study measures the enrichment factor of BTx in K. brevis algal aerosol. During red-tide events in 2021 and 2022, aerosol and water samples were collected from Gulf Coast beaches in Southwest Florida with various levels of K. brevis growth. The concentrations of BTx in SSA were measured using an enzyme-linked immunosorbent assay kit. The concentrations of both aerosolized BTx and organic matter (OM) were normalized using that of sodium ions and were shown to be significantly higher than those observed in seawater. Lipophilic BTx is present in SSA at concentrations that are 2-4 orders of magnitude higher than seawater, and 1-2 orders of magnitude higher than concentrations of OM in SSA. Enrichment of aerosolized BTx was also simulated in the algal culture tank with two different aerosol generation methods. The estimated activity coefficient (order of 1019) of BTx in bulk seawater using the inorganic thermodynamic model indicates very poor solubility of BTx in seawater and supports its enrichment in ocean surfaces and SSA. Examining the enrichment factors of BTx and organic matter in SSA contributes to our comprehension of the potential respiratory challenges posed by inhaled algal aerosols during red tide occurrences. In addition, enriched BTx in the uppermost layer of the ocean during red tide blooms can adversely influence animals that inhabit in tide flats with neurological and respiratory impacts.
more »
« less
- Award ID(s):
- 2044921
- PAR ID:
- 10628491
- Publisher / Repository:
- Environmental Pollution
- Date Published:
- Journal Name:
- Environmental Pollution
- Volume:
- 366
- Issue:
- C
- ISSN:
- 0269-7491
- Page Range / eLocation ID:
- 125474
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
The Impact of Divalent Cations on the Enrichment of Soluble Saccharides in Primary Sea Spray AerosolField measurements have shown that sub-micrometer sea spray aerosol (SSA) is significantly enriched in organic material, of which a large fraction has been attributed to soluble saccharides. Existing mechanistic models of SSA production struggle to replicate the observed enhancement of soluble organic material. Here, we assess the role for divalent cation mediated co-adsorption of charged surfactants and saccharides in the enrichment of soluble organic material in SSA. Using measurements of particle supersaturated hygroscopicity, we calculate organic volume fractions for molecular mimics of SSA generated from a Marine Aerosol Reference Tank. Large enhancements in SSA organic volume fractions (Xorg > 0.2) were observed for 50 nm dry diameter (dp) particles in experiments where cooperative ionic interactions were favorable (e.g., palmitic acid, Mg2+, and glucuronic acid) at seawater total organic carbon concentrations (<1.15 mM C) and ocean pH. Significantly smaller SSA organic volume fractions (Xorg < 1.5 × 10−3) were derived from direct measurements of soluble saccharide concentrations in collected SSA with dry diameters <250 nm, suggesting that organic enrichment is strongly size dependent. The results presented here indicate that divalent cation mediated co-adsorption of soluble organics to insoluble surfactants at the ocean surface may contribute to the enrichment of soluble saccharides in SSA. The extent to which this mechanism explains the observed enhancement of saccharides in nascent SSA depends strongly on the concentration, speciation, and charge of surfactants and saccharides in the sea surface microlayer.more » « less
-
Environmental contextSaccharides contribute substantially to dissolved organic carbon in the ocean and are enriched at the ocean surface. In this study, we demonstrate that saccharides are more enriched in persistent whitecap foam compared to the sea surface. The maturation of bubbles at the air–water interface is thus expected to enhance the enrichment of organic matter at the ocean surface and ultimately in the sea spray aerosol that forms when bubbles burst at the ocean surface. RationaleOrganic matter accumulates at the ocean surface. Herein, we provide the first quantitative assessment of the enrichment of dissolved saccharides in persistent whitecap foam and compare this enrichment to the sea surface microlayer (SSML) during a 9 day mesocosm experiment involving a phytoplankton bloom generated in a Marine Aerosol Reference Tank (MART). MethodologyFree monosaccharides were quantified directly, total saccharides were determined following mild acid hydrolysis and the oligo/polysaccharide component was determined as the difference between total and free monosaccharides. ResultsTotal saccharides contributed a significant fraction of dissolved organic carbon (DOC), accounting for 13% of DOC in seawater, 27% in SSML and 31% in foam. Median enrichment factors (EFs), calculated as the ratio of the concentrations of saccharides relative to sodium in SSML or foam to that of seawater, ranged from 1.7 to 6.4 in SSML and 2.1–12.1 in foam. Based on median EFs, xylitol, mannitol, glucose, galactose, mannose, xylose, fucose, rhamnose and ribose were more enriched in foam than SSML. DiscussionThe greatest EFs for saccharides coincided with high chlorophyll levels, indicating increasing ocean surface enrichment of saccharides during phytoplankton blooms. Higher enrichments of organic matter in sea foam over the SSML indicate that surface active organic compounds become increasingly enriched on persistent bubble film surfaces. These findings help to explain how marine organic matter becomes highly enriched in sea spray aerosol that is generated by bursting bubbles at the ocean surface.more » « less
-
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.more » « less
-
Abstract Atmospheric deposition represents a major input for micronutrient trace elements (TEs) to the surface ocean and is often quantified indirectly through measurements of aerosol TE concentrations. Sea spray aerosol (SSA) dominates aerosol mass concentration over much of the global ocean, but few studies have assessed its contribution to aerosol TE loading, which could result in overestimates of “new” TE inputs. Low‐mineral aerosol concentrations measured during the U.S. GEOTRACES Pacific Meridional Transect (GP15; 152°W, 56°N to 20°S), along with concurrent towfish sampling of surface seawater, provided an opportunity to investigate this aspect of TE biogeochemical cycling. Central Pacific Ocean surface seawater Al, V, Mn, Fe, Co, Ni, Cu, Zn, and Pb concentrations were combined with aerosol Na data to calculate a “recycled” SSA contribution to aerosol TE loading. Only vanadium was calculated to have a SSA contribution averaging >1% along the transect (mean of 1.5%). We derive scaling factors from previous studies on TE enrichments in the sea surface microlayer and in freshly produced SSA to assess the broader potential for SSA contributions to aerosol TE loading. Maximum applied scaling factors suggest that SSA could contribute significantly to the aerosol loading of some elements (notably V, Cu, and Pb), while for others (e.g., Fe and Al), SSA contributions largely remained <1%. Our study highlights that a lack of focused measurements of TEs in SSA limits our ability to quantify this component of marine aerosol loading and the associated potential for overestimating new TE inputs from atmospheric deposition.more » « less
An official website of the United States government
