Marine microalgae support world fisheries production and influence climate through various mechanisms. They are also responsible for harmful blooms that adversely impact coastal ecosystems and economies. Optimal growth and survival of many bloom-forming microalgae, including climatically important dinoflagellates and coccolithophores, requires the close association of specific bacterial species, but the reasons for these associations are unknown. Here, we report that several clades of Marinobacter ubiquitously found in close association with dinoflagellates and coccolithophores produce an unusual lower-affinity dicitrate siderophore, vibrioferrin (VF). Fe-VF chelates undergo photolysis at rates that are 10–20 times higher than siderophores produced by free-living marine bacteria, and unlike the latter, the VF photoproduct has no measurable affinity for iron. While both an algal-associated bacterium and a representative dinoflagellate partner, Scrippsiella trochoidea , used iron from Fe-VF chelates in the dark, in situ photolysis of the chelates in the presence of attenuated sunlight increased bacterial iron uptake by 70% and algal uptake by >20-fold. These results suggest that the bacteria promote algal assimilation of iron by facilitating photochemical redox cycling of this critical nutrient. Also, binary culture experiments and genomic evidence suggest that the algal cells release organic molecules that are used by the bacteria for growth. Such mutualistic sharing of iron and fixed carbon has important implications toward our understanding of the close beneficial interactions between marine bacteria and phytoplankton, and the effect of these interactions on algal blooms and climate.

Gymnodinium catenatum is one of several dinoflagellates that produce a suite of neurotoxins called the paralytic shellfish toxins (PST), responsible for outbreaks of paralytic shellfish poisoning in temperate and tropical waters. Previous research suggested that the bacteria associated with the surface of the sexual resting stages (cyst) were important to the production of PST by G. catenatum. This study sought to characterise the cultivable bacterial diversity of seven different strains of G. catenatum that produce both high and abnormally low amounts of PST, with the long-term aim of understanding the role the bacterial flora has in bloom development and toxicity of this alga. Sixty-one bacterial isolates were cultured and phylogenetically identified as belonging to the Proteobacteria (70%), Bacteroidetes (26%) or Actinobacteria (3%). The Alphaproteobacteria were the most numerous both in terms of the number of isolates cultured (49%) and were also the most abundant type of bacteria in each G. catenatum culture. Two phenotypic (functional) traits inferred from the phylogenetic data were shown to be a common feature of the bacteria present in each G. catenatum culture: firstly, Alphaproteobacteria capable of aerobic anoxygenic photosynthesis, and secondly, Gammaproteobacteria capable of hydrocarbon utilisation and oligotrophic growth. In relation to reports of autonomous production of PST by dinoflagellate-associated bacteria, PST production by bacterial isolates was investigated, but none were shown to produce any PST-like toxins. Overall, this study has identified a number of emergent trends in the bacterial community of G. catenatum which are mirrored in the bacterial flora of other dinoflagellates, and that are likely to be of especial relevance to the population dynamics of natural and harmful algal blooms.

A range of bubble and sea spray aerosol generators has been tested in the laboratory and compared with oceanic measurements from the literature. We have shown that the method of generation has a significant influence on the properties of the aerosol particles produced. Hence, the validity of a generation system to mimic atmospheric aerosol is dependent on its capacity for generating bubbles and particles in a realistic manner. A bubble-bursting aerosol generator which produces bubbles by water impingement was shown to best reproduce the oceanic bubble spectral shapes, which confirms previous findings. Two porous bubblers and a plunging-water jet system were tested as bubble-bursting aerosol generators for comparison with a standard nebulizer. The methods for aerosol production were evaluated by analysing the bubble spectrum generated by the bubble-bursting systems and the submicron size distribution, hygroscopicity and cloud condensation nucleus activity of the aerosols generated by the different techniques. Significant differences in the bubble spectrum and aerosol properties were observed when using different aerosol generators. The aerosols generated by the different methods exhibited similar hygroscopicity and cloud condensation nucleus activity behaviour when a sample of purely inorganic salts was used as a parent seawater solution; however, significant differences in the aerosol properties were found when using samples of filtered natural seawater enriched with biogenic organics. The presence of organics in the aerosol caused suppression of the growth factor at humidities above 75% RH and an increase in the critical supersaturation with respect to the generation from artificial seawater devoid of organics. The extent of the effect of organics on the aerosol properties varied depending on the method of particle production. The results of this work indicate that the aerosol generation mechanism affects the particles organic enrichment, thus the behaviour of the produced aerosols strongly depends on the laboratory aerosol generator employed. Comparison between bubble lifetimes in several laboratory simulations and the oceanic conditions indicated that it would require a considerable extension of the dimensions of the currently used bubble-bursting laboratory systems in order to replicate the characteristic oceanic bubble lifetimes. We analyzed the implications derived from the reduced bubble residence times in scaled systems, regarding marine surfactants adsorption on rising bubbles, and found that adsorption equilibrium is reached on a timescale much shorter than the bubble lifetime in small-scale laboratory generators. This implies that adsorption of marine surface-active material is not limited by surfactant transport to the bubble surface.

The effect of biogenic dissolved and colloidal organic matter on the production of submicron primary sea-spray aerosol was investigated via the simulation of bubble bursting in seawater enriched with phytoplankton-released organics. Seawater samples collected along a transect off the West African coast during the RHaMBLe cruise (RRS Discovery cruise D319), conducted as part of the SOLAS UK program, were analysed in order to identify the dominant oceanic algal species in a region of high biological activity. Cultures of microalgal strains representative of the species found in the collected seawater were grown in order to produce natural bioexudate. Colloidal plus dissolved organic fraction in this material remaining after <0.2 μm filtration was employed to prepare organic-enriched seawater proxies for the laboratory production of marine aerosol using a plunging-waterjet system as an aerosol generator. Submicron size distributions of aerosols generated from different organic monolayers and seawater proxies enriched with biogenic exudate were measured and compared with blanks performed with artificial seawater devoid of marine organics. A shift of the aerosol submicron size distribution toward smaller sizes and an increase in the production of particles with dry diameter (D_p0)175 μM was required to observe a significant impact on the size distribution, which implies that effects are expected to be substantial only in high biological activity areas abundant with diatom algal populations. The laboratory findings were in agreement with analogous bubble-bursting experiments conducted with unfiltered oceanic seawater collected during the RHaMBLe cruise, which revealed a higher production of particles with D_p0<100 nm at regions with high biological activity. These findings suggest that the increase in the atmospheric aerosol modal sizes from winter to summer, reported by long-term observations in North Atlantic waters, is not directly due to an impact of the higher primary organic matter production occurring during warm periods. A novel sub-micrometric size-resolved source flux function, explicitly defined as a function of the diatomaceous exudate concentration, was derived from the size distribution measurements and the estimation of the fractional whitecap coverage. According to the defined parameterisation, a 300 μM OC_{<0.2 μm} concentration of diatomaceous exudate in seawater produces an overall increment in the total source particle flux of ~20% with respect to the organics-free seawater case. The effect increases with decreasing particle size for D_p0<100 nm, resulting in multiplicative factors between 1.02–2 with respect to the particle flux generated from seawater devoid of marine organics. The total source flux derived from the presented parameterisation was compared to recent definitions of sea-spray source fluxes based on laboratory and field observations in the literature.

The effect of nanogel colloidal and dissolved organic matter <0.2 μm, secreted by marine biota, on the hygroscopic growth and droplet activation behaviour of the primary marine aerosol was studied. Seawater proxies were prepared by the combination of artificial seawater devoid of marine organics and natural seawater enriched in organic exudate released by laboratory-grown phytoplankton cultures, as described in a companion paper. The primary aerosol was produced by bubble bursting, using a plunging multijet system as an aerosol generator. The aerosol generated from seawater proxies enriched with marine exudate presented organic volume fractions on the order of 8–37%, as derived by applying a simple mixing rule. The hygroscopic growth and cloud condensation nuclei (CCN) activity of the marine organics-enriched particles where 9–17% and 5–24% lower, respectively, than those of the aerosol produced from artificial seawater devoid of exudate. Experiments in a companion paper indicated that the cloud nuclei formation could be enhanced in diatom bloom areas because of the increase in the primary particle production induced by marine organics. The experiments in the present study, however, indicate that the impacts of such an enhancement would be counteracted by the reduction in the CCN activity of the primary particles enriched in marine organics. The extent of the effect of the biogenic matter on the particle behaviour was dependent on the seawater organic concentration and type of algal exudate. Aerosol produced from seawater proxies containing diatomaceous exudate presented higher hydrophobicity and lower CCN activity than those enriched with nanoplankton exudate. The organic fraction of the particles was found to correlate with the seawater organic concentration, without observing saturation of the particle organic mass fraction even for unrealistically high organic matter concentration in seawater. These findings are indicative that discrepancies on the composition of the primary aerosol between different studies could partly be explained by the difference in the nature and concentration of the organic matter in the source seawater employed. Consistently across the experiments, theoretical analysis based on the Köhler model predicted a reduction in the primary marine aerosol CCN activity upon the incorporation of marine organics into the particle composition. This effect is consequence of the replacement of small inorganic sea salt molecules by large molar mass organic molecules, together with a moderate suppression of the surface tension at the point of activation of 5–0.5%, which leads to a dominance of the reduction in the dissolved solute in the Raoult term.