Emissions of Fe(II) and its kinetic of oxidation at Tagoro submarine volcano, El Hierro

The eruptive process that took place in October 2011 in the submarine volcano Tagoro off the Island of El Hierro and the subsequent degasification stage, five months later, have increased the concentration of TdFe(II) (Total dissolved iron(II)) in thewaters nearest to the volcanic edifice. In order to detect any variation in concentrations of TdFe(II) due to hydrothermal emissions, three cruiseswere carried out two years after the eruptive process in October 2013,March 2014 andMay 2015. The results fromthese cruises confirmed important positive anomalies in TdFe(II), which coincided with negatives anomalies in pHF,is (pH in free scale, at in situ conditions) located in the proximity of themain cone. Maximumvalues in TdFe(II) both at the surface, associated to chlorophyll a maximum, and at the sea bottom, were also observed, showing the important influence of organic complexation and particle re-suspension processes. Temporal variability studies were carried out over periods ranging from hours to days in the stations located over themain and two secondary cones in the volcanic edifice with positive anomalies in TdFe(II) concentrations and negative anomalies in pHF,is values. Observations showed an important variability in both pHF,is and TdFe(II) concentrations, which indicated the volcanic area was affected by a degasification process that remained in the volcano after the eruptive phase had ceased. Fe(II) oxidation kinetic studies were also undertaken in order to analyze the effects of the seawater properties in the proximities of the volcano on the oxidation rate constants and t1/2 (half-life time) of ferrous iron. The increased TdFe(II) concentrations and the low associated pHF,is values acted as an important fertilization event in the seawater around the Tagoro volcano at the Island of El Hierro providing optimal conditions for the regeneration of the area.En prens

Carbon dioxide system in the Canary region during October 1995

During the cruise F/S Poseidon 212/3 (September 30-October 8, 1995) determination of carbon system variables was carried out over the section of La Palma-La Graciosa and at the ESTOC station in the Canary Island area. Total alkalinity and pH in the total scale at 25 degreesC were determined at 24 stations from surface to bottom. In this area, the presence of different water masses can be traced by the carbon system variables. NACW is defined by a strong gradient of A(T) and pH from 150 to 750 m. MW is characterised by high values of A(T) and pH between 1000 to 1200 in and AAIW signals are found at around 900 in in the strait between Gran Canaria and Fuerteventura with low A(T), low pH and a maximum of fCO(2). Assuming an atmospheric mean value of fCO(2) of 360 mu atm and an average surface value of 393 +/-7 mu atm, we can conclude that during this cruise this oceanic area tends to release CO2 into the atmosphere, acting as a weak source with a carbon flux towards the atmosphere of +8.0 +/-1.8 mmol.m(-2)d(-1). The saturation levels in the Canary Island area have been found to be higher than 3600 m for calcite and 2700 in for aragonite. The inorganic carbon/organic carbon ratio (IC/OC) varies from 0.07 at 300 m to 0.5 at 3000 m. The IC/OC ratio shows that about a 34% increase in the C-T of the deep water is contributed by the inorganic CaCO3 dissolution. The IC at 300 in is around 7 mu mol kg(-1), increasing with depth to 37.5 mu mol kg(-1) at 3700 m

Regional differences in modelled net production and shallow remineralization in the North Atlantic subtropical gyre

© The Author(s), 2012. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 9 (2012): 2831-2846, doi:10.5194/bg-9-2831-2012.We used 5-yr concomitant data of tracer distribution from the BATS (Bermuda Time-series Study) and ESTOC (European Station for Time-Series in the Ocean, Canary Islands) sites to build a 1-D tracer model conservation including horizontal advection, and then compute net production and shallow remineralization rates for both sites. Our main goal was to verify if differences in these rates are consistent with the lower export rates of particulate organic carbon observed at ESTOC. Net production rates computed below the mixed layer to 110 m from April to December for oxygen, dissolved inorganic carbon and nitrate at BATS (1.34±0.79 mol O2 m−2, −1.73±0.52 mol C m−2 and −125±36 mmol N m−2) were slightly higher for oxygen and carbon compared to ESTOC (1.03±0.62 mol O2 m−2, −1.42±0.30 mol C m−2 and −213±56 mmol N m−2), although the differences were not statistically significant. Shallow remineralization rates between 110 and 250 m computed at ESTOC (−3.9±1.0 mol O2 m−2, 1.53±0.43 mol C m−2 and 38±155 mmol N m−2) were statistically higher for oxygen compared to BATS (−1.81±0.37 mol O2 m−2, 1.52±0.30 mol C m−2 and 147±43 mmol N m−2). The lateral advective flux divergence of tracers, which was more significant at ESTOC, was responsible for the differences in estimated oxygen remineralization rates between both stations. According to these results, the differences in net production and shallow remineralization cannot fully explain the differences in the flux of sinking organic matter observed between both stations, suggesting an additional consumption of non-sinking organic matter at ESTOC.B. Mourino was supported by the Ramon y Cajal program from the Spanish Minister of Science and Technology. Funding for this study was provided by the Xunta de Galicia under the research project VARITROP (09MDS001312PR, PI B. Mourino) and by the Ministerio de Ciencia e Innovation MOMAC project (CTM2008-05914/MAR)

Variability of nutrients and carbon dioxide in the Antarctic Intermediate Water between 1990 and 2014

Antarctic Intermediate Water (AAIW) formation constitutes an important mechanism for the export of macronutrients out of the Southern Ocean that fuels primary production in low latitudes. We used quality-controlled gridded data from five hydrographic cruises between 1990 and 2014 to examine decadal variability in nutrients and dissolved inorganic carbon (DIC) in the AAIW (neutral density range 27 < γ n <  27.4) along the Prime Meridian. Significant positive trends were found in DIC (0.70 ± 0.4 μmol kg− 1 year− 1) and nitrate (0.08 ± 0.06 μ mol kg− 1 year− 1) along with decreasing trends in temperature (− 0.015 ± 0.01∘C year− 1) and salinity (− 0.003 ± 0.002 year− 1) in the AAIW. Accompanying this is an increase in apparent oxygen utilization (AOU, 0.16 ± 0.07 μ mol kg− 1 year− 1). We estimated that 75% of the DIC change has an anthropogenic origin. The remainder of the trends support a scenario of a strengthening of the upper-ocean overturning circulation in the Atlantic sector of the Southern Ocean in response to the positive trend in the Southern Annular Mode. A decrease in net primary productivity (more nutrients unutilized) in the source waters of the AAIW could have contributed as well but cannot fully explain all observed changes

Reconstruction of the seasonal cycle of air–sea CO2 fluxes in the Strait of Gibraltar

The present study reports and discusses water surface fCO2 measurements from 36 cruises in the Strait of Gibraltar made over an eleven-year period (1997 to 2009). Underway measurements of sea surface CO2 fugacity (fCO2sw), sea surface temperature (SST) and sea surface salinity (SSS) compiled during the cruises were analysed and integrated into a single database which provided the resolution/sensitivity required for an examination of the seasonal variability of the fCO2sw; these data allowed the reconstruction of the climatological seasonal cycle for the year 2005. The seasonal cycle of both SST and SSS was found to be within the range of the thermohaline signature of the North Atlantic Surface Water, which is the main water mass that flows into the Mediterranean Sea through the Strait of Gibraltar at the surface. The seasonal distribution of fCO22005 was characterised by a monthly minimum value of 334 ± 12 μatm in May, followed by a gradual increase to a maximum of 385 μatm during late summer, due to the warming of surface waters. The spatial variability of fCO2sw observed in the area also indicated that superimposed phenomena, occurring at scales other than seasonal, could affect the dissolved CO2 distribution. In particular, intense vertical mixing processes generated by internal waves in this region may have an impact on the surface fCO2sw on a tidal scale. Seasonal CO2 cycle dynamics indicated that the surface waters of the Strait of Gibraltar acted as an atmospheric CO2 source during summer and autumn and a CO2 sink during winter and spring. When these sink/source strengths are integrated on an annual basis, the Strait of Gibraltar was close to equilibrium with atmospheric CO2, resulting in a neutral atmosphere-ocean exchange (− 0.06 ± 0.12 mol C m− 2 yr− 1).Funding for this work was provided by the CARBOOCEAN IP of the European Commission (511176GOCE) and by the Spanish Ministry of Education and Sciences through the Projects CAIBEX (CTM2007-66408) and (CTM2006-26206-E/MAR). Author Mercedes de la Paz acknowledges the financial support of the CSIC postdoctoral program JAE-Doc.Peer reviewe

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

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A global monthly climatology of oceanic total dissolved inorganic carbon: a neural network approach

Anthropogenic emissions of CO2 to the atmosphere have modified the carbon cycle for more than 2 centuries. As the ocean stores most of the carbon on our planet, there is an important task in unraveling the natural and anthropogenic processes that drive the carbon cycle at different spatial and temporal scales. We contribute to this by designing a global monthly climatology of total dissolved inorganic carbon (TCO2), which offers a robust basis in carbon cycle modeling but also for other studies related to this cycle. A feedforward neural network (dubbed NNGv2LDEO) was configured to extract from the Global Ocean Data Analysis Project version 2.2019 (GLODAPv2.2019) and the Lamont–Doherty Earth Observatory (LDEO) datasets the relations between TCO2 and a set of variables related to the former's variability. The global root mean square error (RMSE) of mapping TCO2 is relatively low for the two datasets (GLODAPv2.2019: 7.2 µmol kg−1; LDEO: 11.4 µmol kg−1) and also for independent data, suggesting that the network does not overfit possible errors in data. The ability of NNGv2LDEO to capture the monthly variability of TCO2 was testified through the good reproduction of the seasonal cycle in 10 time series stations spread over different regions of the ocean (RMSE: 3.6 to 13.2 µmol kg−1). The climatology was obtained by passing through NNGv2LDEO the monthly climatological fields of temperature, salinity, and oxygen from the World Ocean Atlas 2013 and phosphate, nitrate, and silicate computed from a neural network fed with the previous fields. The resolution is 1∘×1∘ in the horizontal, 102 depth levels (0–5500 m), and monthly (0–1500 m) to annual (1550–5500 m) temporal resolution, and it is centered around the year 1995. The uncertainty of the climatology is low when compared with climatological values derived from measured TCO2 in the largest time series stations. Furthermore, a computed climatology of partial pressure of CO2 (pCO2) from a previous climatology of total alkalinity and the present one of TCO2 supports the robustness of this product through the good correlation with a widely used pCO2 climatology (Landschützer et al., 2017). Our TCO2 climatology is distributed through the data repository of the Spanish National Research Council (CSIC; https://doi.org/10.20350/digitalCSIC/10551, Broullón et al., 2020)

Estoc: New approach warrants long-term support to the oceanic observational program

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Significant Release of Dissolved Inorganic Nutrients From the Shallow Submarine Volcano Tagoro (Canary Islands) Based on Seven-Year Monitoring

Tagoro, the shallow submarine volcano that erupted south of El Hierro (Canary Islands, Spain) in October 2011, has been intensely monitored for over 7 years, from the early eruptive stage to the current degassing stage characterized by moderate hydrothermal activity. Here, we present a detailed study of the emissions of inorganic macronutrients (NO2– + NO3–, PO4, and Si(OH)4) comprising a dataset of over 3300 samples collected through three different sampling methodologies. Our results show a significant nutrient enrichment throughout the whole studied period, up to 8.8-fold (nitrate), 4.0-fold (phosphate), and 16.3-fold (silicate) in the water column, and larger enrichments of phosphate (10.5-fold) and silicate (325.4-fold), but not of nitrate, in the samples collected directly from the vents. We also provide some preliminary results showing ammonium (NH4+) concentrations up to 1.97 μM in the vent fluids as compared to 0.02 μM in the surrounding waters. Nutrient fluxes from the volcano during the degassing stage were estimated as 3.19 ± 1.17 mol m–2 year–1 (NO2– + NO3–), 0.02 ± 0.01 mol m–2 year–1 (PO4), and 0.60 ± 1.35 mol m–2 year–1 (Si(OH)4), comparable to other important nutrient sources in the region such as fluxes from the NW-African upwelling. Nutrient ratios were affected, with a minimum (NO3– + NO2–):PO4 ratio of 2.36:1; moreover, a linear correlation between silicate and temperature enabled the use of this nutrient as a mixing tracer. This study sheds light on how shallow hydrothermal systems impact the nutrient-poor upper waters of the ocean.En prens

Fe(II) stability in coastal seawater during experiments in Patagonia, Svalbard, and Gran Canaria

The speciation of dissolved iron (DFe) in the ocean is widely assumed to consist almost exclusively of Fe(III)-ligand complexes. Yet in most aqueous environments a poorly defined fraction of DFe also exists as Fe(II), the speciation of which is uncertain. Here we deploy flow injection analysis to measure in situ Fe(II) concentrations during a series of mesocosm/microcosm/multistressor experiments in coastal environments in addition to the decay rate of this Fe(II) when moved into the dark. During five mesocosm/microcosm/multistressor experiments in Svalbard and Patagonia, where dissolved (0.2 µm) Fe and Fe(II) were quantified simultaneously, Fe(II) constituted 24 %–65 % of DFe, suggesting that Fe(II) was a large fraction of the DFe pool. When this Fe(II) was allowed to decay in the dark, the vast majority of measured oxidation rate constants were less than calculated constants derived from ambient temperature, salinity, pH, and dissolved O2. The oxidation rates of Fe(II) spikes added to Atlantic seawater more closely matched calculated rate constants. The difference between observed and theoretical decay rates in Svalbard and Patagonia was most pronounced at Fe(II) concentrations <2 nM, suggesting that the effect may have arisen from organic Fe(II) ligands. This apparent enhancement of Fe(II) stability under post-bloom conditions and the existence of such a high fraction of DFe as Fe(II) challenge the assumption that DFe speciation in coastal seawater is dominated by ligand bound-Fe(III) species