Sea-Air Transfer of Ostreopsis Phycotoxins Is Driven by the Chemical Diversity of the Particulate Fraction in the Surface Microlayer.

Blooms of Ostreopsis cf. ovata pose an emerging health threat, causing respiratory disorders in various coastal regions. This dinoflagellate produce potent phycotoxins named ovatoxins that can be transferred from the seawater to the atmosphere. However, the biotic and abiotic conditions affecting their transfer are still unknown. In this study, we investigate the sea-to-air transfer of O. cf ovata phycotoxins using a process study in an aerosol reference tank (MART) and field observations. The process study exhibited a positive correlation between the phycotoxin content in sea spray aerosol (up to 832.59 ng m-3) and the particulate phycotoxin fraction in the water column and surface microlayer. In contrast, in the natural system, aerosolized phycotoxins were only observed in one out of six air collection (total toxins 0.59 ng m-3) despite optimal wind conditions. In both the process study and the natural system, ovatoxins represented only a minor fraction of the total toxin content, which was comprised of up to 90% liguriatoxins. In seawater, while no solubilized ovatoxins were detected, the concentration in dissolved liguriatoxin-a reached up to 19.07 µg L-1. These results underscore the need for future research on the liguriatoxins, and on their toxicity to establish safe exposure thresholds for beachgoers.

Unraveling the Marine Microplastic Cycle: The First Simultaneous Data Set for Air, Sea Surface Microlayer, and Underlying Water.

Microplastics (MP) including tire wear particles (TWP) are ubiquitous. However, their mass loads, transport, and vertical behavior in water bodies and overlying air are never studied simultaneously before. Particularly, the sea surface microlayer (SML), a ubiquitous, predominantly organic, and gelatinous film (<1 mm), is interesting since it may favor MP enrichment. In this study, a remote-controlled research catamaran simultaneously sampled air, SML, and underlying water (ULW) in Swedish fjords of variable anthropogenic impacts (urban, industrial, and rural) to fill these knowledge gaps in the marine-atmospheric MP cycle. Polymer clusters and TWP were identified and quantified with pyrolysis-gas chromatography-mass spectrometry. Air samples contained clusters of polyethylene terephthalate, polycarbonate, and polystyrene (max 50 ng MP m-3). In water samples (max. 10.8 µg MP L-1), mainly TWP and clusters of poly(methyl methacrylate) and polyethylene terephthalate occurred. Here, TWP prevailed in the SML, while the poly(methyl methacrylate) cluster dominated the ULW. However, no general MP enrichment was observed in the SML. Elevated anthropogenic influences in urban and industrial compared to the rural fjord areas were reflected by enhanced MP levels in these areas. Vertical MP movement behavior and distribution were not only linked to polymer characteristics but also to polymer sources and environmental conditions.

Mercury (Hg) in the "Skin" of the Ocean: Dissolved Gaseous Hg, Total Hg, and Hg Redox Chemistry in Sea Surface Microlayer and Implication for Air-Sea Hg Exchange.

The sea surface microlayer (SML) is the uppermost ∼1000 µm of the surface of the ocean. With distinct physicochemical properties and position relative to the adjacent subsurface waters (SSWs), the ubiquitous distribution and high dynamics of the SML greatly regulate the global air-sea gas exchange and biogeochemistry. Mercury (Hg) redox chemistry in surface seawaters and air-sea exchange of gaseous Hg (mainly Hg(0)) fundamentally control the global oceanic Hg cycle. However, the occurrence and transformation of Hg in the SML have been poorly quantified. Here we optimize the traditional SML sampling system to make it more suitable for dissolved gaseous Hg (DGM, mainly Hg(0)) sampling. We then assess the temporal and spatial variability of DGM, total Hg, dissolved organic carbon (DOC), and Hg redox chemistry in the SML and SSWs of diverse marine environments. Our data suggest a general DGM, total Hg, and DOC enrichment in the SML relative to the SSWs but with complex variability in time and space. The incubation experiments further reveal the complex characteristics of Hg redox chemistry between the SML and SSWs. We discuss important implications of the SML Hg cycle on air-sea Hg exchange and suggest wider investigations of the SML Hg cycle in the global hydrosphere.

Isotopic Insights into Organic Composition Differences between Supermicron and Submicron Sea Spray Aerosol.

To elucidate the seawater biological and physicochemical factors driving differences in organic composition between supermicron and submicron sea spray aerosol (SSAsuper and SSAsub), carbon isotopic composition (δ13C) measurements were performed on size-segregated, nascent SSA collected during a phytoplankton bloom mesocosm experiment. The δ13C measurements indicate that SSAsuper contains a mixture of particulate and dissolved organic material in the bulk seawater. After phytoplankton growth, a greater amount of freshly produced carbon was observed in SSAsuper with the proportional contribution being modulated by bacterial activity, emphasizing the importance of the microbial loop in controlling the organic composition of SSAsuper. Conversely, SSAsub exhibited no apparent relationship with biological activity but tracked closely with surface tension measurements probing the topmost ∼0.2-1.5 µm of the sea surface microlayer. This probing depth is similar to a bubble's film thickness at the ocean surface, suggesting that SSAsub organic composition may be influenced by the presence of surfactants at the air-sea interface that are transferred into SSAsub by bubble bursting. Our findings illustrate the substantial impact of seawater dynamics on the pronounced organic compositional differences between SSAsuper and SSAsub and demonstrate that these two SSA populations should be considered separately when assessing their contribution to marine aerosols and climate.

A floating chamber system for VOC sea-to-air flux measurement near the sea surface.

Volatile organic compounds (VOCs) form ozone (O3) and secondary organic aerosols (SOAs) in the atmosphere under favourable conditions. Biogenic VOC levels in the marine atmosphere are significantly lower compared with levels in the atmosphere above terrestrial ecosystems. However, much less is known about the marine biogenic VOC sea-to-air flux, specifically at the sea surface level. Therefore, here we describe a newly developed and cost-effective floating chamber system that has the capacity to measure the VOC sea-to-air flux near the sea surface (< 1 m). The floating chamber is coupled with adsorbent cartridges, and samples were analysed in the laboratory using commercial thermal desorption and gas chromatography mass spectrometry (TD-GC-MS). The structural performance of the floating flux chamber was evaluated, and it was shown to have the capacity to stay continuously afloat for up to 72 h in various conditions (e.g., rainy, windy) and with wave heights up to approximately 1 m in coastal waters. Preliminary measurements of isoprene (3-Methyl-1,2-butadiene) (C5H8) sea-to-air flux using the floating flux chamber in the coastal waters off the east coast of Peninsular Malaysia found values in the region of 107 molecules/cm2/s, comparable with most published values based on various flux measurement techniques. We suggest the proposed floating chamber system could serve as a cost-effective VOC flux technique that allows measurements near the sea surface.

Sea Spray Aerosols Contain the Major Component of Human Lung Surfactant.

Marine phytoplankton influence the composition of sea spray aerosols (SSAs) by releasing various compounds. The biogenic surfactant dipalmitoylphosphatidylcholine (DPPC) is known to accumulate in the sea surface microlayer, but its aerosolization has never been confirmed. We conducted a 1 year SSA sampling campaign at the Belgian coast and analyzed the SSA composition. We quantified DPPC at a median and maximum air concentration of 7.1 and 33 pg m-3, respectively. This discovery may be of great importance for the field linking ocean processes to human health as DPPC is the major component of human lung surfactant and is used as excipient in medical aerosol therapy. The natural airborne exposure to DPPC seems too low to induce direct human health effects but may facilitate the effects of other marine bioactive compounds. By analyzing various environmental variables in relation to the DPPC air concentration, using a generalized linear model, we established that wave height is a key environmental predictor and that it has an inverse relationship. We also demonstrated that DPPC content in SSAs is positively correlated with enriched aerosolization of Mg2+ and Ca2+. In conclusion, our findings are not only important from a human health perspective but they also advance our understanding of the production and composition of SSAs.

The Role of Extracellular Carbonic Anhydrase in Biogeochemical Cycling: Recent Advances and Climate Change Responses.

Climate change has been predicted to influence the marine phytoplankton community and its carbon acquisition strategy. Extracellular carbonic anhydrase (eCA) is a zinc metalloenzyme that catalyses the relatively slow interconversion between HCO3- and CO2. Early results indicated that sub-nanomolar levels of eCA at the sea surface were sufficient to enhance the oceanic uptake rate of CO2 on a global scale by 15%, an addition of 0.37 Pg C year-1. Despite its central role in the marine carbon cycle, only in recent years have new analytical techniques allowed the first quantifications of eCA and its activity in the oceans. This opens up new research areas in the field of marine biogeochemistry and climate change. Light and suitable pH conditions, as well as growth stage, are crucial factors in eCA expression. Previous studies showed that phytoplankton eCA activity and concentrations are affected by environmental stressors such as ocean acidification and UV radiation as well as changing light conditions. For this reason, eCA is suggested as a biochemical indicator in biomonitoring programmes and could be used for future response prediction studies in changing oceans. This review aims to identify the current knowledge and gaps where new research efforts should be focused to better determine the potential feedback of phytoplankton via eCA in the marine carbon cycle in changing oceans.

Pseudomonas neustonica sp. nov., isolated from the sea surface microlayer of the Ross Sea (Antarctica).

Gram-stain-negative, aerobic and rod-shaped bacterial strains, designated SSM26T and SSM44, were isolated from a sea surface microlayer sample from the Ross Sea, Antarctica. Analysis of the 16S rRNA gene sequences of strains SSM26T and SSM44 revealed a clear affiliation with the genus Pseudomonas. Based on the results of phylogenetic analysis, strains SSM26T and SSM44 showed the closest phylogenetic relationship with the species Pseudomonas sabulinigri KCTC 22137T with the 16S rRNA gene sequence similarity level of 98.5 %. Strains SSM26T and SSM44 grew optimally at 30 °C, pH 7.0-7.5 and 0.5-10.0 % NaCl (w/v). The major cellular fatty acids were C18 : 1 ω7c (31.3-34.9 %), C16 : 0 (15.5-20.2 %), summed feature 3 (C16 : 1 ω7c/C16 : 1 ω6c; 19.5-25.4 %) and C12 : 0 (6.0-9.3 %). The genomic DNA G+C content of each strain was 56.2 mol%. Genomic relatedness analyses based on the average nucleotide identity and the genome-to-genome distance showed that strains SSM26T and SSM44 constituted a single species that was clearly distinguishable from its phylogenetically close relatives. The combined phenotypic, chemotaxonomic, genomic and phylogenetic data also showed that strains SSM26T and SSM44 could be distinguished from validly published members of the genus Pseudomonas. Thus, these strains should be classified as representing a novel species in the genus Pseudomonas, for which the name Pseudomonas neustonica sp. nov. is proposed with the type strain SSM26T (=KCCM 43193T=JCM 31284T=PAMC 28426T) and a sister strain SSM44 (=KCCM 43194=JCM 31285=PAMC 28427).

Sandaracinobacter neustonicus sp. nov., isolated from the sea surface microlayer in the Southwestern Pacific Ocean, and emended description of the genus Sandaracinobacter.

A Gram-stain-negative, non-motile, facultatively anaerobic and rod-shaped bacterial strain, designated PAMC 28131T, was isolated from a sea surface microlayer sample in the open water of the Pacific Ocean. Phylogenetic analysis of the 16S rRNA gene sequence of strain PAMC 28131T revealed an affiliation to the genus Sandaracinobacter with the closest species Sandaracinobacter sibiricus RB16-17T (sequence similarity of 98.2 %). Strain PAMC 28131T was able to grow optimally with 0.5-1.0 % NaCl and at pH 6.5-7.0 and 30 °C. The polar lipids were phosphatidylglycerol, phosphatidylethanolamine, two unidentified phospholipids, an unidentified aminolipid, an unidentified glycolipid and an unidentified lipid. The major cellular fatty acids (>10 %) were C18 : 1 ω6c and/or C18 : 1 ω7c, (42.6 %), C17 : 1 ω6c (19.3 %) and C16 : 1 ω6c and/or C16 : 1 ω7c (15.8 %), and the respiratory quinone was Q-10. The genomic DNA G+C content was 65.3 mol%. The phylogenetic, phenotypic and chemotaxonomic data showed that strain PAMC 28131T could be clearly distinguished from S. sibiricus RB16-17T. Thus, strain PAMC 28131T should be classified as representing a novel species in the genus Sandaracinobacter, for which the name Sandaracinobacter neustonicus sp. nov. is proposed. The type strain is PAMC 28131T (=KCCM 43127T=JCM 30734T).

Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer.

Summertime Arctic shipboard observations of oxygenated volatile organic compounds (OVOCs) such as organic acids, key precursors of climatically active secondary organic aerosol (SOA), are consistent with a novel source of OVOCs to the marine boundary layer via chemistry at the sea surface microlayer. Although this source has been studied in a laboratory setting, organic acid emissions from the sea surface microlayer have not previously been observed in ambient marine environments. Correlations between measurements of OVOCs, including high levels of formic acid, in the atmosphere (measured by an online high-resolution time-of-flight mass spectrometer) and dissolved organic matter in the ocean point to a marine source for the measured OVOCs. That this source is photomediated is indicated by correlations between the diurnal cycles of the OVOC measurements and solar radiation. In contrast, the OVOCs do not correlate with levels of isoprene, monoterpenes, or dimethyl sulfide. Results from box model calculations are consistent with heterogeneous chemistry as the source of the measured OVOCs. As sea ice retreats and dissolved organic carbon inputs to the Arctic increase, the impact of this source on the summer Arctic atmosphere is likely to increase. Globally, this source should be assessed in other marine environments to quantify its impact on OVOC and SOA burdens in the atmosphere, and ultimately on climate.

Cystobasidium keelungensis sp. nov., a novel mycosporine producing carotenogenic yeast isolated from the sea surface microlayer in Taiwan.

Cystobasidium keelungensis SN2T (CBS 6949 = BCRC 920080), a new anamorphic basidiomycetous yeast species, is described in this paper. The strains belonging to this species were isolated from the sea surface microlayer and underlying water in Taiwan. These strains were identified by examining nucleotide sequences in the species-specific D1/D2 domains of the large subunit (LSU) ribosomal RNA (rRNA) and by evaluating their physiological characteristics. Phylogenetic analyses of D1/D2 sequences revealed that C. keelungensis was most closely related to the species C. slooffiae (LSU rRNA gene sequence divergence of 1.5%), and it belonged to the Erythrobasidium clade. No sexual reproduction was observed. This species differed from related species in carbon and nitrogen assimilation patterns and growth at 35 °C. Screening C. keelungensis for the presence of UV-absorbing compounds showed that mycosporine-glutaminol-glucoside and mycosporine-glutamicol-glucoside (maximum absorption: 310 nm) were the major UV-absorbing compounds, which differ from the compounds present in some freshwater yeast strains reported in previous studies. After UV induction, SN2 had a higher level of mycosporine production than other carotenogenic yeasts in this study.

Sea surface microlayer and elemental composition in phaeo-, chloro-, and rhodophytes in winter and spring.

Trace metal or rare earth element (REE) content of marine macroalgae are underexamined and there is a great need for further understanding since macroalgae are used for food and may also be bioindicators of environmental changes. This study, by using high resolution inductive coupled plasma spectrometer in a clean laboratory (class 1000), investigates the trace metal and REE concentrations and composition in the youngest tissue of various species within three algal classes in the Trondheimsfjord, Norway, comprising phaeo-, chloro-, and rhodophytes in winter (February) and Spring (May) 2013, with the main focus on phaeophytes. The macroalgae were found in a clear zonation pattern as a function of depth. A significant difference in element concentration and composition was found between the six phaeophyte species along with a significant difference between winter and spring tissue. A zonation depth trend in algal tissue element concentration was also found for the phaeophytes, where the algal species located in both extreme ends (upper vs. lower littoral zone) obtained a lower element concentration than the algae located in the middle part of the littoral zone. This trend seems to result from different algal contact with the metal-rich sea surface microlayer. The chlorophytes had 5-27 times higher concentration of REE and lead (Pb) than the two other algal classes. Results indicate that the rhodo- and chlorophytes are better accumulators than the phaeophytes for several trace metals and REE.

Alkaline phosphatase activity in the phosphorus-limited southern Chinese coastal waters.

Three fractions of alkaline phosphatase activity (APA), including phytoplankton APA (phyto-APA), bacterial APA (bact-APA), and free-APA, were examined in the sea surface microlayer (SML) and the subsurface water (SSW) from Daya Bay, Guishan Island, and Guanghai Bay of southern China. Relationships between APA and environmental parameters were analyzed. The growth of phytoplankton was significantly limited by dissolved inorganic phosphorus (DIP) in the three sea areas, especially in Daya Bay. Total-APA ranged between 1.41 and 35.26 nmol/L/hr, and the highest value was found in Daya Bay. The increased APA in Daya Bay was the result of the increase of phytoplankton biomass and the response of phytoplankton to P limitation. Phyto-APA was the main contributor in Daya Bay, while phyto- and free-APA co-dominated in Guishan Island and Guanghai Bay. Bact-, phyto-, and total-APA showed a significant inverse power function relationship with DIP, and 0.2 µmol/L was the threshold for DIP on particulates and total-APA. Pearson correlation analysis suggested that DIP limitation together with high N levels enhanced APA. High water temperature and freshwater input accelerated APA as well. Principal component analysis clearly separated samples from the three sea areas, as well as from the SML and the SSW, which indicated the differences in environmental parameters and APA levels. Our results highlight the influence of phosphorus limitation and environmental parameters on APA.

Amylibacter kogurei sp. nov., a novel marine alphaproteobacterium isolated from the coastal sea surface microlayer of a marine inlet.

A novel Gram-negative bacterium, designated 4G11T, was isolated from the sea surface microlayer of a marine inlet. On the basis of 16S rRNA gene sequence analysis, the strain showed the closest similarity to Amylibacter ulvae KCTC 32465T (99.0 %). However, DNA-DNA hybridization values showed low DNA relatedness between strain 4G11T and its close phylogenetic neighbours, Amylibacter marinus NBRC 110140T (8.0±0.4 %) and Amylibacter ulvae KCTC 32465T (52.9±0.9 %). Strain 4G11T had C18 : 1, C16 : 0 and C18 : 2 as the major fatty acids. The only isoprenoid quinone detected for strain 4G11T was ubiquinone-10. The major polar lipids were phosphatidylglycerol, phosphatidylcholine, one unidentified polar lipid, one unidentified phospholipid and one unidentified aminolipid. The DNA G+C content of strain 4G11T was 50.0 mol%. Based on phenotypic and chemotaxonomic characteristics and analysis of the 16S rRNA gene sequence, the novel strain should be assigned to a novel species, for which the name Amylibacter kogurei sp. nov. is proposed. The type strain of Amylibacter kogurei is 4G11T (KY463497=KCTC 52506T=NBRC 112428T).

Warming and Inhibition of Salinization at the Ocean's Surface by Cyanobacteria.

This paper describes high-resolution in situ observations of temperature and, for the first time, of salinity in the uppermost skin layer of the ocean, including the influence of large surface blooms of cyanobacteria on those skin properties. In the presence of the blooms, large anomalies of skin temperature and salinity of 0.95°C and -0.49 practical salinity unit were found, but a substantially cooler (-0.22°C) and saltier skin layer (0.19 practical salinity unit) was found in the absence of surface blooms. The results suggest that biologically controlled warming and inhibition of salinization of the ocean's surface occur. Less saline skin layers form during precipitation, but our observations also show that surface blooms of Trichodesmium sp. inhibit evaporation decreasing the salinity at the ocean's surface. This study has important implications in the assessment of precipitation over the ocean using remotely sensed salinity, but also for a better understanding of heat exchange and the hydrologic cycle on a regional scale.

Co-occurrence of microplastics and microparticles containing Cu and Zn and other heavy metals in sea-surface microlayer in Osaka Bay, Japan.

Antifouling biocides such as Cu, Zn, and organic compounds not only inhibit adhesion of sessile organisms on ship hull but also possess toxicity to non-sessile organisms in marine environment. Thus, we firstly investigated the heavy metals and polymer types of anthropogenic microparticles (MPs) floating in the sea-surface microlayer (S-SML) in Osaka Bay. 7 types of MPs containing different metals (Cu, Cu-Zn, Zn, Ti, Sn, Ba and Fe-Mn-Ni) were found. The polymer type for 97.8 % of Cu and Cu-Zn MPs (41 samples) and 52.6 % of Zn MPs (19 samples) was acrylic resins which are widely used as binders in contemporary antifouling paints for ships; concentrations of 511-54,000 mg/kg for Cu and 95.1-13,200 mg/kg for Zn were found in these MPs. The high metal concentrations found the co-existence of acrylic polymers point towards an origin from antifouling paint particles (APPs). Furthermore, to quantify Cu and Zn concentrations in these MPs based on X-ray fluorescence spectroscopy (µ-XRF), calibration curves obtained from standard paint particles containing different Cu and Zn concentrations and different particle sizes made with similar matrix used in commercial antifouling paint were firstly established, according to which highly reliable Cu and Zn concentrations in MPs were obtained.

Vertical distribution and risk assessment of pharmaceuticals and other micropollutants in southern North Sea coastal waters.

Pharmaceutical compounds are micropollutants of emerging concern, as well as other classes of chemicals such as UV filters and artificial sweeteners. They enter marine environments via wastewater treatment plants, aquaculture runoff, hospital effluents, and shipping activities. While many studies have investigated the presence and distribution of these pollutants in numerous coastal areas, our study is the first to focus on their occurrence, spatial distribution, and vertical distribution in the sea surface microlayer (SML) and the near-surface layer of marine environments. We analyzed 62 pharmaceutical compounds, one UV filter, and six artificial sweeteners from the SML to the corresponding underlying water (0 cm, 20 cm, 50 cm, 100 cm, and 150 cm) at four stations in the southern North Sea. One station is the enclosed Jade Bay, one is the Weser estuary at Bremerhaven, and the other two stations (NS_7 and NS_8) are in the open German Bight. Jade Bay receives pollutants from surrounding wastewater treatment plants, while the Weser estuary receives pollutants from cities like Bremerhaven, which has dense populations and industrial activities. Concentrations of pharmaceutical compounds were higher in the upper water layers (from the SML to 20 cm). Eleven pharmaceutical compounds (caffeine, carbamazepine, gemfibrozil, ibuprofen, metoprolol, salicylic acid, clarithromycin, novobiocin, clindamycin, trimethoprim, and tylosin) were detected in >95 % of our samples. One UV filter (benzophenone-4) was found in 83 % and three artificial sweeteners (acesulfame, saccharin, and sucralose) in 100 % of all our samples. All artificial sweeteners posed high risks to the freshwater invertebrate Daphnia magna. Understanding the spatial and vertical distribution of pharmaceuticals and other micropollutants in marine environments may be essential in assessing their dispersal and detection in other aquatic environments.

How do open coastal fire episodes' impact sea surface microlayer neuston communities?

Human-induced climate change is expected to increase the frequency and severity of vegetation fires. The Mediterranean region is considered particularly prone to fire episodes in summer. It is well known that pyrogenic particles are an important source of external nutrients for the marine environment, especially in oligotrophic areas. In this study, the plankton components of the sea surface layers were integrated to evaluate, for the first time, their dynamics over six months and their response to fire events in a typical coastal area of the Adriatic Sea. Concentrations of nutrients and organic compounds, together with plankton communities were significantly higher in the sea surface microlayer (SML, < 1 mm thick), than in the underlying water from 1 m depth. The piconeuston community and chlorophyll a responded with extreme abundance and concentration to the most intense fire event that enriched the SML with NH4+. Phytoneuston abundance increased with a delay of 2 weeks, while diversity indices decreased slightly after the fire events. The large abundances of the studied piconeuston parameters could be explained by the high availability of organic compounds and the immediate availability of NH4+, while the phytoneuston community responded to an increased NO3- concentration, triggered by the fire events. We confirmed that fast-acting marine heterotrophs are important members of biogeochemical cycles associated with fire events and that, together with phytoplankton, they are unavoidable parameters to detect environmental changes.

Highly active bacterial DMSP metabolism in the surface microlayer of the eastern China marginal seas.

The microbial cycling of dimethylsulfoniopropionate (DMSP) and the resulting gaseous catabolites dimethylsulfide (DMS) or methylmercaptan (MeSH) play key roles in the global sulfur cycle and potentially climate regulation. As the ocean-atmosphere boundary, the sea surface microlayer (SML) is important for the generation and emission of DMS and MeSH. However, understanding of the microbial DMSP metabolism remains limited in the SML. Here, we studied the spatiotemporal differences for DMS/DMSP, bacterial community structure and the key bacterial DMSP metabolic genes between SML and subsurface seawater (SSW) samples in the eastern China marginal seas (the East China Sea and Yellow Sea). In general, DMSPd and DMSPt concentrations, and the abundance of total, free-living and particle-associated bacteria were higher in SML than that in SSW. DMSP synthesis (~7.81-fold for dsyB, ~2.93-fold for mmtN) and degradation genes (~5.38-fold for dmdA, ~6.27-fold for dddP) detected in SML were more abundant compared with SSW samples. Free-living bacteria were the main DMSP producers and consumers in eastern Chinese marginal sea. Regionally, the bacterial community structure was distinct between the East China Sea and the Yellow Sea. The abundance of DMSP metabolic genes (dsyB, dmdA, and dddP) and genera in the East China Sea were higher than those of the Yellow Sea. Seasonally, DMSP/DMS level and DMSP metabolic genes and bacteria were more abundant in SML of the East China Sea in summer than in spring. Different from those in spring, Ruegeria was the dominant DMSP metabolic bacteria. In conclusion, the DMSP synthesis and degradation showed significant spatiotemporal differences in the SML of the eastern China marginal seas, and were consistently more active in the SML than in the SSW.

Marine plastics alter the organic matter composition of the air-sea boundary layer, with influences on CO2 exchange: a large-scale analysis method to explore future ocean scenarios.

Microplastics are substrates for microbial activity and can influence biomass production. This has potentially important implications in the sea-surface microlayer, the marine boundary layer that controls gas exchange with the atmosphere and where biologically produced organic compounds can accumulate. In the present study, we used six large scale mesocosms to simulate future ocean scenarios of high plastic concentration. Each mesocosm was filled with 3 m3 of seawater from the oligotrophic Sea of Crete, in the Eastern Mediterranean Sea. A known amount of standard polystyrene microbeads of 30 µm diameter was added to three replicate mesocosms, while maintaining the remaining three as plastic-free controls. Over the course of a 12-day experiment, we explored microbial organic matter dynamics in the sea-surface microlayer in the presence and absence of microplastic contamination of the underlying water. Our study shows that microplastics increased both biomass production and enrichment of carbohydrate-like and proteinaceous marine gel compounds in the sea-surface microlayer. Importantly, this resulted in a ∼3 % reduction in the concentration of dissolved CO2 in the underlying water. This reduction was associated to both direct and indirect impacts of microplastic pollution on the uptake of CO2 within the marine carbon cycle, by modifying the biogenic composition of the sea's boundary layer with the atmosphere.