Chemistry and Release of Gases from the Surface Ocean

The sea-surface layer is the very upper part of the sea surface where reduced mixing leads to strong gradients in physical, chemical and biological properties1. This surface layer is naturally reactive, containing a complex chemistry of inorganic components and dissolved organic matter (DOM), the latter including amino acids, proteins, fatty acids, carbohydrates, and humic-type components,2 with a high proportion of functional groups such as carbonyls, carboxylic acids and aromatic moieties.3 The different physical and chemical properties of the surface of the ocean compared with bulk seawater, and its function as a gateway for molecules to enter the atmosphere or ocean phase, make this an interesting and important region for study. A number of chemical reactions are believed to occur on and in the surface ocean; these may be important or even dominant sources or sinks of climatically-active marine trace gases. However the sea surface, especially the top 1um to 1mm known as the sea surface microlayer (ssm), is critically under-sampled, so to date much of the evidence for such chemistry comes from laboratory and/or modeling studies. This review discusses the chemical and physical structure of the sea surface, mechanisms for gas transfer across it, and explains the current understanding of trace gas formation at this critical interface between the ocean and atmosphere.

Modelling the vertical distribution of eggs of anchovy (Engraulis encrasicolus) and sardine (Sardina pilchardus)

Measurements were made of the density and settling velocity of eggs of sardine (Sardina pilchardus) and anchovy (Engraulis encrasicolus), using a density-gradient column. These results were related to observed vertical distributions of eggs obtained from stratified vertical distribution sampling in the Bay of Biscay. Eggs of both species had slightly positive buoyancy in local seawater throughout most of their development until near hatching, when there was a marked increase in density and they became negatively buoyant. The settling velocity of anchovy eggs, which are shaped as prolate ellipsoids, was close to predictions for spherical particles of equivalent volume. An improved model was developed for prediction of the settling velocity of sardine eggs, which are spherical with a relatively large perivitelline volume; this incorporated permeability of the chorion and adjustment of the density of the perivitelline fluid to ambient seawater. Eggs of both species were located mostly in the top 20 m of the water column, in increasing abundance towards the surface. A sub-surface peak of egg abundance was sometimes observed at the pycnocline, particularly where this was pronounced and associated with a low-salinity surface layer. There was a progressive deepening of the depth distributions for successive stages of egg development. Results from this study can be applied for improved plankton sampling of sardine and anchovy eggs and in modelling studies of their vertical distribution.

Buoyancy measurements and vertical distribution of eggs of sardine (Sardina pilchardus) and anchovy (Engraulis encrasicolus)

Measurements were made of the density and settling velocity of eggs of sardine (Sardina pilchardus) and anchovy (Engraulis encrasicolus), using a density-gradient column. These results were related to observed vertical distributions of eggs obtained from stratified vertical distribution sampling in the Bay of Biscay. Eggs of both species had slightly positive buoyancy in local seawater throughout most of their development until near hatching, when there was a marked increase in density and they became negatively buoyant. The settling velocity of anchovy eggs, which are shaped as prolate ellipsoids, was close to predictions for spherical particles of equivalent volume. An improved model was developed for prediction of the settling velocity of sardine eggs, which are spherical with a relatively large perivitelline volume; this incorporated permeability of the chorion and adjustment of the density of the perivitelline fluid to ambient seawater. Eggs of both species were located mostly in the top 20 m of the water column, in increasing abundance towards the surface. A sub-surface peak of egg abundance was sometimes observed at the pycnocline, particularly where this was pronounced and associated with a low-salinity surface layer. There was a progressive deepening of the depth distributions for successive stages of egg development. Results from this study can be applied for improved plankton sampling of sardine and anchovy eggs and in modelling studies of their vertical distribution.

Discovery of a SAR11 growth requirement for thiamin’s pyrimidine precursor and its distribution in the Sargasso Sea

Vitamin traffic, the production of organic growth factors by some microbial community members and their use by other taxa, is being scrutinized as a potential explanation for the variation and highly connected behavior observed in ocean plankton by community network analysis. Thiamin (vitamin B1), a cofactor in many essential biochemical reactions that modify carbon-carbon bonds of organic compounds, is distributed in complex patterns at subpicomolar concentrations in the marine surface layer (0-300 m). Sequenced genomes from organisms belonging to the abundant and ubiquitous SAR11 clade of marine chemoheterotrophic bacteria contain genes coding for a complete thiamin biosynthetic pathway, except for thiC, encoding the 4-amino-5-hydroxymethyl-2-methylpyrimidine (HMP) synthase, which is required for de novo synthesis of thiamin's pyrimidine moiety. Here we demonstrate that the SAR11 isolate 'Candidatus Pelagibacter ubique', strain HTCC1062, is auxotrophic for the thiamin precursor HMP, and cannot use exogenous thiamin for growth. In culture, strain HTCC1062 required 0.7 zeptomoles per cell (ca. 400 HMP molecules per cell). Measurements of dissolved HMP in the Sargasso Sea surface layer showed that HMP ranged from undetectable (detection limit: 2.4 pM) to 35.7 pM, with maximum concentrations coincident with the deep chlorophyll maximum. In culture, some marine cyanobacteria, microalgae and bacteria exuded HMP, and in the Western Sargasso Sea, HMP profiles changed between the morning and evening, suggesting a dynamic biological flux from producers to consumers.

The combined effects of seasonal community succession and adaptive algal physiology on lipid profiles of coastal phytoplankton in the western English channel

Lipids are key constituents of marine phytoplankton, and some fatty acids (key constituents of lipids) are essential dietary components for secondary producers. However, in natural marine ecosystems the interactions of factors affecting seasonal phytoplankton lipid composition are still poorly understood. The aim of this study was to assess the roles of seasonal succession in phytoplankton community composition and nutrient concentrations, on the lipid composition of the phytoplankton community. Fatty acid and polar lipid composition in seston was measured in surface waters at the time series station L4, an inshore station in the Western English Channel, from January to December 2013. Redundancy analyses (RDA) were used to identify factors (abiotic and biotic) that explained the seasonal variability in phytoplankton lipids. RDA demonstrated that nutrients (namely nitrogen) explained the majority of variation in phytoplankton lipid composition, as well as a smaller explanatory contribution from changes in phytoplankton community composition. The physiological adaptations of the phytoplankton community to nutrient deplete conditions during the summer season when the water column was stratified, was further supported by changes in the polar lipid to phytoplankton biomass ratios (also modelled with RDA) and increases in the lipid to chlorophyll a ratios, which are both indicative of nutrient stress. However, the association of key fatty acid markers with phytoplankton groups e.g. 22:6 n-3 and dinoflagellate biomass (predominant in summer), meant there were no clear seasonal differences in the overall degree of fatty acid saturation, as might have been expected from typical nutrient stress on phytoplankton. Based on the use of polyunsaturated fatty acids (PUFA) as markers of ‘food quality’ for grazers, our results suggest that in this environment high food quality is maintained throughout summer, due to seasonal succession towards flagellated phytoplankton species able to maintain PUFA synthesis under surface layer nutrient depletion.

Coastal upwelling and downwelling forcing of circulation in a semi-enclosed bay: Ria de Vigo

Semi-enclosed bays in upwelling regions are exposed to forcing related to winds, currents and buoyancy over the shelf. The influence of this external forcing is moderated by factors such as connectivity to the open ocean, shelter by surrounding topography, dimensions of the bay, and freshwater outflows. Such bays, preferred locations for ports, mariculture, marine industry, recreational activities and coastal settlement, present a range of characteristics, understanding of which is necessary to their rational management. Observations in such a semi-enclosed bay, the Ria de Vigo in Spain, are used to characterize the influence of upwelling and downwelling pulses on its circulation. In this location, near the northern limit of the Iberian upwelling system, upwelling events dominate during a short summer season and downwelling events the rest of the year. The ria response to the external forcing is central to nutrient supply and resultant plankton productivity that supports its high level of cultured mussel production. Intensive field studies in September 2006 and June 2007 captured a downwelling event and an upwelling event, respectively. Data from eight current profiler moorings and boat-based MiniBat/ADCP surveys provided an unprecedented quasi-synoptic view of the distribution of water masses and circulation patterns in any ria. In the outer ria, circulation was dominated by the introduction of wind-driven alongshore flow from the external continental shelf through the ria entrances and its interaction with the topography. In the middle ria, circulation was primarily related to the upwelling/downwelling cycle, with a cool, salty and dense lower layer penetrating to the inner ria during upwelling over the shelf. A warmer, lower salinity and less dense surface layer of coastal waters flowed inward during downwelling. Without external forcing, the inner ria responded primarily to tides and buoyancy changes related to land runoff. Under both upwelling and downwelling conditions, the flushing of the ria involved shelf responses to wind pulses. Their persistence for a few days was sufficient to allow waters from the continental shelf to penetrate the innermost ria. Longer term observations supported by numerical modeling are required to confirm the generality of such flushing events in the ria and determine their typical frequency, while comparative studies should explore how these scenarios fit into the range of conditions experienced in other semi-enclosed bays.

Tidal and wind influences on circulation in the southern mouth of the Ría de Vigo (NW Iberian Peninsula)

Tidal and wind influences on the velocity field in the Ría de Vigo were assessed using atmospheric data from two meteorological stations located at Bouzas port and on an oceanic buoy off Silleiro Cape along with oceanic data from an ADCP moored in the Ría for a 72-day period. A two-layer circulation pattern was observed. Near-surface and near-bottom currents are primarily influenced by wind (especially remote winds), separated by an intermediate layer dominated by tidal variability. At subtidal frequencies, residual currents are well correlated with wind variability. Remote wind forcing exhibited a markedly high correlation with surface layer currents, indicating the major role played by wind in the long-term upwelling-modulated circulation of the Ría.

Tidal and wind influences on circulation in the southern mouth of the Ría de Vigo (NW Iberian Peninsula)

Tidal and wind influences on the velocity field in the Ría de Vigo were assessed using atmospheric data from two meteorological stations located at Bouzas port and on an oceanic buoy off Silleiro Cape along with oceanic data from an ADCP moored in the Ría for a 72-day period. A two-layer circulation pattern was observed. Near-surface and near-bottom currents are primarily influenced by wind (especially remote winds), separated by an intermediate layer dominated by tidal variability. At subtidal frequencies, residual currents are well correlated with wind variability. Remote wind forcing exhibited a markedly high correlation with surface layer currents, indicating the major role played by wind in the long-term upwelling-modulated circulation of the Ría.

Fine scale variability in methanol uptake and oxidation in the micro-layer and near-surface waters of the Atlantic

The aim of this research was to make the first depth profiles of the microbial assimilation of methanol carbon and its oxidation to carbon dioxide and use as an energy source from the microlayer to 1000 m. Some of the highest reported methanol oxidation rate constants of 0.5–0.6 d−1 were occasionally found in the microlayer and immediately underlying waters (10 cm depth), albeit these samples also showed the greatest heterogeneity compared to other depths down to 1000 m. Methanol uptake into the particulate phase was exceptionally low in microlayer samples, suggesting that any methanol utilised by microbes in this environment is for energy generation. The sea surface microlayer and 10 cm depth also showed a higher proportion of bacteria with a low DNA content, and bacterial leucine uptake rates in surface microlayer samples were either less than or the same as those in the underlying 10 cm layer. The average methanol oxidation and particulate rates were however statistically the same throughout the depths sampled, although the latter were highly variable in the near-surface 0.25–2 m compared to deeper depths. The statistically significant relationship demonstrated between uptake of methanol into particles and bacterial leucine incorporation suggests that many heterotrophic bacteria could be using methanol carbon for cellular growth. On average, methanol bacterial growth efficiency (BGEm) in the top 25 m of the water column is 6% and decreases with depth. Although, for microlayer and 10 cm-depth samples, BGEm is less than the near-surface 25–217 cm, possibly reflecting increased environmental UV stress resulting in increased maintenance costs, i.e. energy required for survival. We conclude that microbial methanol uptake rates, i.e. loss from seawater, are highly variable, particularly close to the seawater surface, which could significantly impact upon seawater concentrations and hence the air–sea flux.