Silicate electrochemical measurements in seawater: chemical and analytical aspects towards a reagentless sensor

From the study of molybdenum oxidation in aqueous solutions we developed a semi-autonomous method to detect silicate in aqueous samples. Molybdenum oxidation was used to form molybdate in acidic media. The silicomolybdic complex formed with silicate is detectable by amperometry or cyclic voltammetry. The new electrochemical method is in good agreement with the method conventionally used for environmental water silicate analysis. In the second stage, a completely reagentless method was developed using molybdate and proton produced during molybdenum oxidation. Reproducibility tests show a precision of 2.6% for a concentration of 100 μmol L−1. This new method will be very suitable for the development of new autonomous silicate sensors easy to handle and without reagents. In this paper we present the analytical and chemical aspects necessary for a complete documentation of the method before the development of a new reagentless sensor

Sensitivity of ecosystem parameters to simulated satellite ocean color data using a coupled physical-biological model of the North Atlantic

A means of assimilating simulated satellite ocean color data with a coupled physical-biological model of the North Atlantic Ocean is implemented, allowing the relative sensitivities of different biological parameters to those data to be investigated. The model consists of an eddy-permitting general circulation model derived from the WOCE Community Modeling Effort and a nitrogen-based, four-compartment NPZD marine ecosystem model. Many of the parameters in marine ecosystem models are poorly known and via assimilation, we hope to better constrain their values. The control parameters chosen for the variational assimilation are the model parameters involved in parameterizations of recycling as these are the most poorly known. Simulated observations are taken while following several floats seeded in varying dynamical biogeochemical provinces of the North Atlantic model domain over a six-month period. Twin experimental results show that, for the given functional forms of growth, mortality and grazing, the following parameters can be successfully recovered from simulated satellite ocean color data: nitrate and detrital recycling parameters in the trade wind domain, zooplankton parameters at higher latitudes (westerly wind and polar domains), and the phytoplankton mortality rate in all regions. By simultaneously assimilating ocean color data in different biological provinces, it becomes possible to successfully constrain all ecosystem parameters at once

Modeling δ15N evolution: First palaeoceanographic applications in a coastal upwelling system

The δ15N signal in marine sediments appears to be a good palaeoceanographic tracer. It records biological processes in the water column and is transferred to and preserved in the sediments. Changes in forcing factors in upwelling systems may be recorded by δ15N. These forcing conditions can be of a biogeochemical nature, such as the initial isotopic signal of the nutrients or the trophic structure, or of a physical nature, such as wind stress, insolation, temperature or dynamic recycling. A simple nitrogen-based trophic chain model was used to follow the development of the nitrogen isotopic signal in nutrients, phytoplankton, zooplankton and detritus. Detrital δ15N, influenced by the isotopic signature of the upwelled nutrients and isotopic fractionation along the trophic chain (photosynthesis and zooplankton excretion), was then compared to the sedimentary signal measured off Mauritania. In our model, the biological variables are transported at shallow depths by a simple circulation scheme perpendicular to the coast depicting a continental shelf recirculation cell. Because cell length depends on the extension of the continental shelf, modifications of the cell length mimic sea level changes. Long cell length (high sea level) scenarios produce higher δ15N values whereas short cell length scenarios result in lower values as in the glacial low sea level periods. Despite changes in many climatic parameters throughout this period, our results show that changing the sea level is sufficient to reconstruct the main pattern of the sedimentary δ15N variations offshore of the Mauritanian upwelling, i.e. an increase from about 3‰ to 7‰ during the deglaciation, without invoking any change in nitrogen fixation or denitrification

Reagentless and calibrationless silicate measurement in oceanic waters

Determination of silicate concentration in seawater without addition of liquid reagents was the key prerequisite for developing an autonomous in situ electrochemical silicate sensor (Lacombe et al., 2007) [11]. The present challenge is to address the issue of calibrationless determination. To achieve such an objective, we chose chronoamperometry performed successively on planar microelectrode (ME) and ultramicroelectrode (UME) among the various possibilities. This analytical method allows estimating simultaneously the diffusion coefficient and the concentration of the studied species. Results obtained with ferrocyanide are in excellent agreement with values of the imposed concentration and diffusion coefficient found in the literature. For the silicate reagentless method, successive chronoamperometric measurements have been performed using a pair of gold disk electrodes for both UME and ME. Our calibrationless method was tested with different concentrations of silicate in artificial seawater from 55 to 140×10−6 mol L−1. The average value obtained for the diffusion coefficient of the silicomolybdic complex is 2.2±0.4×10−6 cm2 s−1, consistent with diffusion coefficient values of molecules in liquid media. Good results were observed when comparing known concentration of silicate with experimentally derived ones. Further work is underway to explore silicate determination within the lower range of oceanic silicate concentration, down to 0.1×10−6 mol L−1

Silicate determination in sea water: toward a reagentless electrochemical method

ilicate has been determined in sea water by four different electrochemical methods based on the detection of the silicomolybdic complex formed in acidic media by the reaction between silicate and molybdenum salts. The first two methods are based on the addition of molybdate and protons in a seawater sample in an electrochemical cell. Cyclic voltammetry presents two reduction and two oxidation peaks giving four values of the concentration and therefore increasing the precision. Then chronoamperometry is performed on an electrode held at a constant potential. A semi-autonomous method has been developed based on the electrochemical anodic oxidation of molybdenum, the complexation of the oxidation product with silicate and the detection of the complex by cyclic voltammetry. This method is tested and compared with the classical colorimetric one during ANT XXIII/3 cruise across Drake Passage (January–February 2006). The detection limit is 1 μM and the deviation between both methods is less than 3% for concentrations higher than 10 μM. Finally a complete reagentless method with a precision of 2.6% is described based on the simultaneous formation of the molybdenum salt and protons in a divided electrochemical cell. This latter method should be very useful for developing a reagentless sensor suitable for long term in situ deployments on oceanic biogeochemical observatories

Spring and winter water mass composition in the Brazil-Malvinas Confluence

Hydrographic data of the Confluence 1 cruise collected during austral spring (November 1988) have been analyzed to estimate relative mixing proportions of the various water masses of the Brazil-Malvinas Confluence region using a multiparameter analysis. Seven source water types (SWT) are identified in this region, and all are retained for the analysis: Thermocline Water (TW), Subantarctic Surface Water (SASW), Antarctic Intermediate Water (AAIW), Upper Circumpolar Deep Water (UCDW), North Atlantic Deep Water (NADW), Lower Circumpolar Deep Water (LCDW) and Weddell Sea Deep Water (WSDW). Tracers selected are temperature, salinity, dissolved oxygen and nutrients. Mixing proportions are quantified and plotted along five zonal sections at 35.4, 36.5, 37.9, 41 and 41.6S. The solution obtained during the springtime cruise is consistent with the wintertime (September 1989) data set (Maamaatuaiahutapu et al., 1992): both show the large local recirculation of AAIW and the separation of NADW from the coast south of the thermocline front. However, noticeable changes in water mass mixing proportions can be detected between the winter of 1989 and the preceding spring. The seasonal change for the upper layers of TW and SASW is related to temporal and spatial fluctuations of the thermohaline front. The marked differences in SWT proportions between the two seasons occur at the same location for TW, SASW and AAIW; suggesting that the upper waters have a large impact on the AAIW movement. The deep waters undergo great spatial changes between the two cruises. The variation of the deep convergence position (revealed by the variation of spatial occupancy of the CDW and NADW) seems influenced by the movement of the thermocline front

Reagentless and silicate interference free electrochemical phosphate determination in seawater

An electrochemical method for phosphate determination in seawater was based on the oxidation of molybdenum in order to form molybdates and protons and subsequently, to create the phosphomolybdic complex electrochemically detectable by means of amperometry at a rotating gold disk electrode [J. Jonca et al., Talanta 87 (2011) 161]. To avoid silicate interferences, the method required an appropriate ratio of protons over molybdates equal to 70. Since the ratio of protons over molybdates created during molybdenum oxidation is only 8, the previous method still needed addition of sulfuric acid and thus was not free from addition of liquid reagents. In the present work, this aspect is solved by modification of the electrochemical cell construction. The method is now totally free from addition of any liquid reagents and gives a possibility to determine phosphate by amperometry in the concentrations range found in the open ocean with a detection limit of 0.11 µM. Having in mind the energy savings for future in situ sensor development, amperometry at rotating gold disk electrode was replaced by differential pulse voltammetry at static one. Phosphate can then be determined with a detection limit of 0.19 µM. Both methods are characterized by good reproducibility with an average measurements precision of 5.7% (amperometry) and 3.8% (differential pulse voltammetry). Results also show a good accuracy with an average deviation from theoretical values of phosphate concentration of 3.1% for amperometry and 3.7% for differential pulse voltammetry

Climatically-Active Gases in the Eastern Boundary Upwelling and Oxygen Minimum Zone (OMZ) Systems

International audienceThe EBUS (Eastern Boundary Upwelling Systems) and OMZs (Oxygen Minimum Zone) contribute very significantly to the gas exchange between the ocean and the atmosphere, notably with respect to the greenhouse gases (hereafter GHG). From in-situ ocean measurements, the uncertainty of the net global ocean-atmosphere CO2 fluxes is between 20 and 30%, and could be much higher in the EBUS-OMZ. Off Peru, very few in-situ data are available presently, which justifies alternative approaches for assessing these fluxes. GHG air-sea fluxes determination can be inferred from inverse modeling applied to Vertical Column Densities (VCDs) from GOSAT, using state of the art modeling, at low spatial resolution. For accurately linking sources of GHGs to EBUS and OMZs, the resolution of the source regions needs to be increased. This task develops on new non-linear and multiscale processing methods for complex signals to infer a higher spatial resolution mapping of the fluxes and the associated sinks and sources between the atmosphere and the ocean. The use of coupled satellite data (e.g. SST and/or Ocean colour) that carry turbulence information associated to ocean dynamics is taken into account at unprecedented detail level to incorporate turbulence effects in the evaluation of the air-sea fluxes. We will present a framework as described above for determining sources and sinks of GHG from satellite remote sensing with the Peru OMZ as a test bed

In search for the sources of plastic marine litter that contaminates the Easter Island Ecoregion

Subtropical gyres are the oceanic regions where plastic litter accumulates over long timescales, exposing surrounding oceanic islands to plastic contamination, with potentially severe consequences on marine life. Islands’ exposure to such contaminants, littered over long distances in marine or terrestrial habitats, is due to the ocean currents that can transport plastic over long ranges. Here, this issue is addressed for the Easter Island ecoregion (EIE). High-resolution ocean circulation models are used with a Lagrangian particle-tracking tool to identify the connectivity patterns of the EIE with industrial fishing areas and coastline regions of the Pacific basin. Connectivity patterns for “virtual” particles either floating (such as buoyant macroplastics) or neutrally-buoyant (smaller microplastics) are investigated. We find that the South American shoreline between 20°S and 40°S, and the fishing zone within international waters off Peru (20°S, 80°W) are associated with the highest probability for debris to reach the EIE, with transit times under 2 years. These regions coincide with the most-densely populated coastal region of Chile and the most-intensely fished region in the South Pacific. The findings offer potential for mitigating plastic contamination reaching the EIE through better upstream waste management. Results also highlight the need for international action plans on this important issue

The Ocean is Losing its Breath: Declining Oxygen in the Worlds Ocean and Coastal Waters

'The Ocean is Losing its Breath' presents a summary of scientific experiments, observations and numerical models addressing the following questions: How has the oxygen content in the open ocean and coastal waters changed over the past century and through geological time? What are the mechanisms behind this oxygen decline? How is ocean oxygen content predicted to change over the rest of the twenty-first century? What are the consequences of low and declining oxygen concentrations in the marine environment? This document was prepared by a group of concerned scientists from across the world, the IOC expert group, the Global Ocean Oxygen Network GO2 NE, established in 2016, which is committed to providing a global and multidisciplinary view on deoxygenation, with a focus on understanding its various aspects and impacts