CO2 fluxes in the Northeast Atlantic Ocean based on measurements from a surface ocean observation platform.

The seasonal and spatial variability of the CO2 system parameters and CO2 air-sea exchange were studied in the Northeast Atlantic Ocean between the northwest African coastal upwelling and the oligotrophic open-ocean waters of the North Atlantic subtropical gyre. Data was collected aboard a volunteer observing ship from February 2019 to February 2020. The seasonal and spatial variability of CO2 fugacity in seawater (fCO2,sw) was strongly driven by the seasonal temperature variation, which increased with latitude and was lower throughout the year in coastal regions where the upwelling and offshore transport was more intense. The thermal to biological effect ratio (T/B) was approximately 2, with minimum values along the African coastline related to higher biological activity in the upwelled waters. The fCO2,sw increased from winter to summer by 11.84 ± 0.28 µatm°C-1 on the inter-island routes and by 11.71 ± 0.25 µatm°C-1 along the northwest African continental shelf. The seasonality of total inorganic carbon normalized to constant salinity of 36.7 (NCT) was studied throughout the region. The effect of biological processes and calcification/dissolution on NCT between February and October represented >90% of the reduction of inorganic carbon while air-sea exchange described <6%. The seasonality of air-sea CO2 exchange was controlled by temperature. The surface waters of the entire region acted as a CO2 sink during the cold months and as a CO2 source during the warm months. The Canary basin acted as a net sink of -0.26 ± 0.04 molC m-2 yr-1. The northwest African continental shelf behaved as a stronger sink at -0.48 ± 0.09 molC m-2 yr-1. The calculated average CO2 flux for the entire area was -2.65 ± 0.44 TgCO2 yr-1 (-0.72 ± 0.12 TgC yr-1).

Significant discharge of CO2 from hydrothermalism associated with the submarine volcano of El Hierro Island.

The residual hydrothermalism associated with submarine volcanoes, following an eruption event, plays an important role in the supply of CO2 to the ocean. The emitted CO2 increases the acidity of seawater. The submarine volcano of El Hierro, in its degasification stage, provided an excellent opportunity to study the effect of volcanic CO2 on the seawater carbonate system, the global carbon flux, and local ocean acidification. A detailed survey of the volcanic edifice was carried out using seven CTD-pH-ORP tow-yo studies, localizing the redox and acidic changes, which were used to obtain surface maps of anomalies. In order to investigate the temporal variability of the system, two CTD-pH-ORP yo-yo studies were conducted that included discrete sampling for carbonate system parameters. Meridional tow-yos were used to calculate the amount of volcanic CO2 added to the water column for each surveyed section. The inputs of CO2 along multiple sections combined with measurements of oceanic currents produced an estimated volcanic CO2 flux = 6.0 10(5) ± 1.1 10(5 )kg d(-1) which is ~0.1% of global volcanic CO2 flux. Finally, the CO2 emitted by El Hierro increases the acidity above the volcano by ~20%.

Effect of Dunaliella tertiolecta organic exudates on the Fe(II) oxidation kinetics in seawater.

The role played by the natural organic ligands excreted by the green algae Dunaliella tertiolecta on the Fe(II) oxidation rate constants was studied at different stages of growth. The concentration of dissolved organic carbon increased from 2.1 to 7.1 mg L(-1) over time of culture. The oxidation kinetics of Fe(II) was studied at nanomolar levels and under different physicochemical conditions of pH (7.2-8.2), temperature (5-35 °C), salinity (10-37), and dissolved organic carbon produced by cells (2.1-7.1 mg L(-1)). The experimental rate always decreased in the presence of organic exudates with respect to that in the control seawater. The Fe(II) oxidation rate constant was also studied in the context of Marcus theory, where ΔG° was 39.31-51.48 kJ mol(-1). A kinetic modeling approach was applied for computing the equilibrium and rate constants for Fe(II) and exudates present in solution, the Fe(II) speciation, and the contribution of each Fe(II) species to the overall oxidation rate constant. The best fit model took into account two acidity equilibrium constants for the Fe(II) complexing ligands with pKa,1=9.45 and pKa,2=4.9. The Fe(II) complexing constants were KFe(II)-LH=3×10(10) and KFe(II)-L=10(7), and the corresponding computed oxidation rates were 68±2 and 36±8 M(-1) min(-1), respectively.

The natural ocean acidification and fertilization event caused by the submarine eruption of El Hierro.

The shallow submarine eruption which took place in October 10(th) 2011, 1.8 km south of the island of El Hierro (Canary Islands) allowed the study of the abrupt changes in the physical-chemical properties of seawater caused by volcanic discharges. In order to monitor the evolution of these changes, seven oceanographic surveys were carried out over six months (November 2011-April 2012) from the beginning of the eruptive stage to the post-eruptive phase. Here, we present dramatic changes in the water column chemistry including large decreases in pH, striking effects on the carbonate system, decreases in the oxygen concentrations and enrichment of Fe(II) and nutrients. Our findings highlight that the same volcano which was responsible for the creation of a highly corrosive environment, affecting marine biota, has also provided the nutrients required for the rapid recuperation of the marine ecosystem.

The submarine volcano eruption at the island of El Hierro: physical-chemical perturbation and biological response.

On October 10 2011 an underwater eruption gave rise to a novel shallow submarine volcano south of the island of El Hierro, Canary Islands, Spain. During the eruption large quantities of mantle-derived gases, solutes and heat were released into the surrounding waters. In order to monitor the impact of the eruption on the marine ecosystem, periodic multidisciplinary cruises were carried out. Here, we present an initial report of the extreme physical-chemical perturbations caused by this event, comprising thermal changes, water acidification, deoxygenation and metal-enrichment, which resulted in significant alterations to the activity and composition of local plankton communities. Our findings highlight the potential role of this eruptive process as a natural ecosystem-scale experiment for the study of extreme effects of global change stressors on marine environments.

Adsorption of copper on Pseudomonas aureofaciens: protective role of surface exopolysaccharides.

Adsorption of copper on exopolysaccharide (EPS)-rich and (EPS)-poor soil rhizospheric Pseudomonas aureofaciens cells was studied as a function of pH and copper concentration at different exposure time in order to assess the effect of cell exopolysaccharides on parameters of adsorption equilibria. The surface properties of bacteria were investigated as a function of pH and ionic strength using potentiometric acid-base titration and electrophoresis that permitted the assessment of the excess surface proton concentration and zeta-potential of the cells, respectively. For adsorption experiments, wide range of Cu concentration was investigated (0.1-375 microM) in order to probe both weak and strong binding sites at the surface. Experimental results were successively fitted using a Linear Programming Model approach. The groups with pK(a) of 4.2-4.8 and from 5.2 to 7.2, tentatively assigned as carboxylates and phosphoryl respectively, are the most abundant at the surface and thus essentially contribute to the metal binding. The presence of exopolysaccharides on the surface decreases the amount of copper adsorbed on the bacterial cell wall apparently via screening the underlining functional groups of the cell wall. At the same time, dissolved EPS substances do not contribute to Cu binding in aqueous solution. Results of this study allow quantification of the role played by the surface EPS matrix as a protective barrier for metal adsorption on bacterial cell walls.