Dissolved iron in the North Atlantic Ocean and Labrador Sea along the GEOVIDE section (GEOTRACES section GA01)

Dissolved Fe (DFe) samples from the GEOVIDE voyage (GEOTRACES GA01, May–June 2014) in the North Atlantic Ocean were analysed using a SeaFAST-picoTM coupled to an Element XR HR-ICP-MS and provided interesting insights on the Fe sources in this area. Overall, DFe concentrations ranged from 0.09 ± 0.01 nmol L−1 to 7.8 ± 0.5 nmol L−1. Elevated DFe concentrations were observed above the Iberian, Greenland and Newfoundland Margins likely due to riverine inputs from the Tagus River, meteoric water inputs and sedimentary inputs. Air-sea interactions were suspected to be responsible for the increase in DFe concentrations within subsurface waters of the Irminger Sea due to deep convection occurring the previous winter, that provided iron-to-nitrate ratios sufficient to sustain phytoplankton growth. Increasing DFe concentrations along the flow path of the Labrador Sea Water were attributed to sedimentary inputs from the Newfoundland Margin. Bottom waters from the Irminger Sea displayed high DFe concentrations likely due to the dissolution of Fe-rich particles from the Denmark Strait Overflow Water and the Polar Intermediate Water. Finally, the nepheloid layers were found to act as either a source or a sink of DFe depending on the nature of particles

Regulation of the phytoplankton heme b iron pool during the North Atlantic spring bloom

CITATION: Louropoulou, E., et al. 2019. Regulation of the phytoplankton heme b iron pool during the North Atlantic spring bloom. Frontiers in Microbiology, 10:1566, doi:10.3389/fmicb.2019.01566.The original publication is available at https://www.frontiersin.orgHeme b is an iron-containing co-factor in hemoproteins. Heme b concentrations are low (0.7 μm) from the North Atlantic Ocean (GEOVIDE cruise – GEOTRACES section GA01), which spanned several biogeochemical regimes. We examined the relationship between heme b abundance and the microbial community composition, and its utility for mapping iron limited phytoplankton. Heme b concentrations ranged from 0.16 to 5.1 pmol L⁻² (median = 2.0 pmol L⁻², n = 62) in the surface mixed layer (SML) along the cruise track, driven mainly by variability in biomass. However, in the Irminger Basin, the lowest heme b levels (SML: median = 0.53 pmol L⁻², n = 12) were observed, whilst the biomass was highest (particulate organic carbon, median = 14.2 μmol L⁻², n = 25; chlorophyll a: median = 2.0 nmol L⁻², n = 23) pointing to regulatory mechanisms of the heme b pool for growth conservation. Dissolved iron (DFe) was not depleted (SML: median = 0.38 nmol L⁻², n = 11) in the Irminger Basin, but large diatoms (Rhizosolenia sp.) dominated. Hence, heme b depletion and regulation is likely to occur during bloom progression when phytoplankton class-dependent absolute iron requirements exceed the available ambient concentration of DFe. Furthermore, high heme b concentrations found in the Iceland Basin and Labrador Sea (median = 3.4 pmol L⁻², n = 20), despite having similar DFe concentrations to the Irminger Basin, were attributed to an earlier growth phase of the extant phytoplankton populations. Thus, heme b provides a snapshot of the cellular activity in situ and could both be used as indicator of iron limitation and contribute to understanding phytoplankton adaptation mechanisms to changing iron supplies.https://www.frontiersin.org/articles/10.3389/fmicb.2019.01566/fullPublisher's versio

Biogeochemical cycle of Iron : distribution and speciation in the North Atlantic Ocean (GA01) and the Southern Ocean (GIpr05) (GEOTRACES)

It is now recognized that iron (Fe) availability dictates the efficiency of the global biological carbon pump such that any perturbation of Fe sources will lead to changes in the carbon cycles with consequences on both other major nutrient cycles and the climate system, controlling about 50% of the worldwide ocean primary production. However, the underlying processes themselves that affect the pathways releasing and trapping Fe, and the relative predominance of Fe sources among the different ocean basins are still poorly constrained. More importantly, the extent to which both the chemical and the physical speciation of Fe are available and accessible for marine organisms, once it enters the ocean, remains uncertain. The reactivity of Fe within the marine environment will depend on its redox and complexation state, with DFe generally considered the most bioavailable form for phytoplankton and Fe-binding organic ligands likely increasing the residence time of Fe that enables enhanced DFe concentrations way above its inorganic solubility in seawater (c.a. 10 pmol L-1).In this context and as part of the international GEOTRACES program, this thesis aims at improving our knowledge on Fe biogeochemical cycle in the ocean and its interactions with the phytoplankton community structure to better constrain the bioavailable forms of Fe. The objectives of this thesis revolve around three scientific questions: 1) What are the distributions, sources, and sinks of dissolved iron? 2) What is the link between the phytoplankton community structure and dissolved iron concentrations? 3) How the organic speciation of dissolved iron affects its concentrations and bioavailability for the phytoplankton community? These three questions were investigated through two contrasted areas: the North Atlantic Ocean (GEOVIDE, GA01 GEOTRACES voyage, PIs G. Sarthou and P. Lherminier) and the Southern Ocean (HEOBI, GIpr05 GEOTRACES voyage, PIs A. Bowie, T. Trull, Z. Chase) the former being occasionally seasonally depleted in Fe, the latter permanently.Il est désormais établi que la disponibilité en fer (Fe) contrôle environ 50% de la production primaire des océans du monde. Cependant, les processus régissant l’intensité des puits et des sources du Fe ainsi que la prédominance relative de ces sources au sein des divers bassins océaniques, sont elles-mêmes peu contraintes. Par ailleurs, une fois entrées dans le système océanique, la disponibilité et l’accessibilité des diverses formes de Fe pour les organismes marins restent incertaines. La réactivité du Fe au sein de l’environnement marin dépend de son état d’oxydoréduction et de complexation. Le fer dissous (DFe) est souvent considéré comme la fraction la plus biodisponible pour le phytoplancton et les ligands organiques du Fe augmentent vraisemblablement le temps de résidence du Fe et permettent des concentrations de DFe bien plus élevées que sa solubilité inorganique ne le permet dans l’eau de mer (10 pmol L-1).Dans ce contexte et s’inscrivant dans le programme international GEOTRACES, cette thèse a pour but principal d’implémenter notre savoir du cycle biogéochimique du Fe dans l’océan et ses interactions avec la structure des communautés phytoplanctoniques, en particulier afin de mieux contraindre les formes biodisponibles du Fe. Ainsi, les objectifs de cette thèse reposent sur trois questions scientifiques : 1) Quelles sont les distributions, sources, et puits de Fe ? 2) Quel est le lien entre la structure des communautés phytoplanctoniques et les concentrations en DFe ? 3) Comment la spéciation organique du DFe impacte ses concentrations et sa biodisponibilité ? Ces trois questions ont été explorées sur de deux zones d’études contrastées : l’océan Nord Atlantique (GEOVIDE, GA01 GEOTRACES voyage, PIs G. Sarthou and P. Lherminier) étant occasionnellement et saisonnièrement appauvri en Fe et l’océan Austral (HEOBI, GIpr05 GEOTRACES voyage, PIs A. Bowie, T. Trull, Z. Chase) l’étant de manière permanente

Etude du cycle biogéochimique du fer : distribution et spéciation dans l’Océan Atlantique Nord (GA01) et l’Océan Austral (GIpr05) (GEOTRACES)

Il est désormais établi que la disponibilité en fer (Fe) contrôle environ 50% de la production primaire des océans du monde. Cependant, les processus régissant l’intensité des puits et des sources du Fe ainsi que la prédominance relative de ces sources au sein des divers bassins océaniques, sont elles-mêmes peu contraintes. Par ailleurs, une fois entrées dans le système océanique, la disponibilité et l’accessibilité des diverses formes de Fe pour les organismes marins restent incertaines. La réactivité du Fe au sein de l’environnement marin dépend de son état d’oxydoréduction et de complexation. Le fer dissous (DFe) est souvent considéré comme la fraction la plus biodisponible pour le phytoplancton et les ligands organiques du Fe augmentent vraisemblablement le temps de résidence du Fe et permettent des concentrations de DFe bien plus élevées que sa solubilité inorganique ne le permet dans l’eau de mer (10 pmol L-1).Dans ce contexte et s’inscrivant dans le programme international GEOTRACES, cette thèse a pour but principal d’implémenter notre savoir du cycle biogéochimique du Fe dans l’océan et ses interactions avec la structure des communautés phytoplanctoniques, en particulier afin de mieux contraindre les formes biodisponibles du Fe. Ainsi, les objectifs de cette thèse reposent sur trois questions scientifiques : 1) Quelles sont les distributions, sources, et puits de Fe ? 2) Quel est le lien entre la structure des communautés phytoplanctoniques et les concentrations en DFe ? 3) Comment la spéciation organique du DFe impacte ses concentrations et sa biodisponibilité ? Ces trois questions ont été explorées sur de deux zones d’études contrastées : l’océan Nord Atlantique (GEOVIDE, GA01 GEOTRACES voyage, PIs G. Sarthou and P. Lherminier) étant occasionnellement et saisonnièrement appauvri en Fe et l’océan Austral (HEOBI, GIpr05 GEOTRACES voyage, PIs A. Bowie, T. Trull, Z. Chase) l’étant de manière permanente.It is now recognized that iron (Fe) availability dictates the efficiency of the global biological carbon pump such that any perturbation of Fe sources will lead to changes in the carbon cycles with consequences on both other major nutrient cycles and the climate system, controlling about 50% of the worldwide ocean primary production. However, the underlying processes themselves that affect the pathways releasing and trapping Fe, and the relative predominance of Fe sources among the different ocean basins are still poorly constrained. More importantly, the extent to which both the chemical and the physical speciation of Fe are available and accessible for marine organisms, once it enters the ocean, remains uncertain. The reactivity of Fe within the marine environment will depend on its redox and complexation state, with DFe generally considered the most bioavailable form for phytoplankton and Fe-binding organic ligands likely increasing the residence time of Fe that enables enhanced DFe concentrations way above its inorganic solubility in seawater (c.a. 10 pmol L-1).In this context and as part of the international GEOTRACES program, this thesis aims at improving our knowledge on Fe biogeochemical cycle in the ocean and its interactions with the phytoplankton community structure to better constrain the bioavailable forms of Fe. The objectives of this thesis revolve around three scientific questions: 1) What are the distributions, sources, and sinks of dissolved iron? 2) What is the link between the phytoplankton community structure and dissolved iron concentrations? 3) How the organic speciation of dissolved iron affects its concentrations and bioavailability for the phytoplankton community? These three questions were investigated through two contrasted areas: the North Atlantic Ocean (GEOVIDE, GA01 GEOTRACES voyage, PIs G. Sarthou and P. Lherminier) and the Southern Ocean (HEOBI, GIpr05 GEOTRACES voyage, PIs A. Bowie, T. Trull, Z. Chase) the former being occasionally seasonally depleted in Fe, the latter permanently

Iron availability influences nutrient drawdown in the Heard and McDonald Islands region, Southern Ocean

WOS:000467669600001International audienceAt the southern part of the northern Kerguelen Plateau (Southern Ocean) is an active volcanic hotspot, hosting volcanically active Heard Island and McDonald Islands (HIMI), the former of which is largely covered by glaciers. While offshore waters are persistently Fe limited, typical of the broader Southern Ocean, near shore waters over the Kerguelen plateau show variability in Fe distributions and support a high biomass of phytoplankton during austral spring-summer. This study investigates dissolved iron (DFe) and macronutrient distributions in waters surrounding HIMI during the Heard Earth-Ocean-Biosphere Interactions (HEOBI) voyage in January-February 2016. Comparison of surface DFe with macronutrient concentrations shows that the majority of the plateau is Fe limited in late summer and, based on comparison with previous voyages, also Fe limited in different years and earlier in the bloom season. The distribution of DFe drawdown from estimated winter inventories to observed late summer inventories shows that DFe availability drives macronutrient uptake on the plateau. The drawdown of silicic acid decreases relative to nitrate drawdown in proximity to HIMI, in agreement with classical diatom nutrient uptake behaviour under iron replete conditions. Comparison of Fe: nitrate and Fe: phosphate drawdown ratios with expected uptake stoichiometry suggest that recycling of Fe increases with distance from Fe sources on the plateau. Lastly, comparison with data from previous voyages shows that DFe distribution varies inter-annually due to complex oceanographic conditions on the plateau, with greatest variability observed over the rough bathymetry and strongly tidally influenced region closest to HIMI. Together these data highlight the central role of Fe in driving nutrient uptake and stoichiometry in the HIMI region of the Kerguelen Plateau

Critical evaluation of a seaFAST system for the analysis of trace metals in marine samples

WOS:000460710200086International audienceA seawater preconcentration system (sPAFAST) with offline sector-field inductively coupled plasma mass spectrometry (SF-ICP-MS) detection was critically evaluated for ultra-low trace elemental analysis of Southern Ocean samples over a four-year period (2015-2018). The commercially available system employs two Nobias PAl resin columns for buffer cleaning and sample preconcentration, allowing salt matrix removal with simultaneous extraction of a range of trace elements. With a primary focus on method simplicity and practicality, a range of experimental parameters relevant to oceanographic analysis were considered, including reduction of blank levels (over weeks and years), instrument conditioning, extraction efficiencies over different pH ranges (5.8-6.4), and preconcentration factors (similar to 10-70 times). Conditions were optimised for the analysis of ten important trace elements (Cd, Co, Cu, Fe, Ga, Mn, Ni, Pb, Ti and Zn) in open ocean seawater samples, and included initial pre-cleaning and conditioning of the seaFAST unit for one week before each separate analytical sequence; a controlled narrow buffer pH of 6.20 +/- 0.02 used for extraction; and a sample preconcentration factor of 10 for (relatively) concentrated rainwater or sea ice, 40 for typical seawater samples, and up to 67 times for seawater samples collected in the remote open ocean such as the Southern Ocean. Method accuracy (both short - days to weeks - and long term - months to years) were evaluated through extensive analysis of a range of oceanographic standard reference samples including SAFe D1 (n = 20), D2 (n = 3), S (n = 15), GEOTRACES GD (n = 6), GSC (n = 42) and GSP (n = 42), as well as NASS-6 (n = 6). Measured values for oceanographic samples were found to agree with consensus values to within +/- 6% for Cd, Cu, Fe, Ni, Pb and Zn. Offsets were noted for Co (labile fraction only; no UV oxidation), Mn (difference also noted in other recent studies) and Ti (limited reference values). No consensus values currently exist for Ga. Iron and Mn in Southern Ocean samples were also independently verified via flow injection analysis methods (R-2 = 0.95, n = 244 (Fe) and 0.92, n = 85 (Mn), paired t-test, p \textless\textless 0.05). Precisions over four years were evaluated through analysis of community seawater samples as well as a range of bulk in-house seawaters (3 sources, each n-100) and acid blanks (n = 250), and were typically found to be within 5-8%, depending on analyte and concentration. Values presented here represent one of the largest independent data sets for these reference samples, as well as the most documented comprehensive suite of GSP and GSC values currently available (consensus values have not yet been released). Samples covering a range of salinities (0-60) were investigated to demonstrate method versatility, with excellent recoveries noted using the seaFAST Nobias PAl column (\textgreater 98% for most elements, with 70-80% for Ga and Ti). By way of example, data is presented showing the application of the method to samples collected on the Kerguelen plateau in the Indian sector of the Southern Ocean (HEOBI voyage, January February 2016) and in land-fast ice and brine collected near Davis station, Antarctica, in austral summer 2015 (with a salinity range from 0 to 73 g kg(-1)). Finally, a range of recommendations for successful implementation of a seaFAST system are provided, along with considerations for future investigation

Dissolved iron in the North Atlantic Ocean and Labrador Sea along the GEOVIDE section (GEOTRACES section GA01)

International audienceDissolved Fe (DFe) samples from the GEOVIDE voyage (GEOTRACES GA01, May–June 2014) in the North Atlantic Ocean were analyzed using a seaFAST-pico™ coupled to an Element XR sector field inductively coupled plasma mass spectrometer (SF-ICP-MS) and provided interesting insights into the Fe sources in this area. Overall, DFe concentrations ranged from 0.09±0.01 to 7.8±0.5 nmol L−1. Elevated DFe concentrations were observed above the Iberian, Greenland, and Newfoundland margins likely due to riverine inputs from the Tagus River, meteoric water inputs, and sedimentary inputs. Deep winter convection occurring the previous winter provided iron-to-nitrate ratios sufficient to sustain phytoplankton growth and lead to relatively elevated DFe concentrations within subsurface waters of the Irminger Sea. Increasing DFe concentrations along the flow path of the Labrador Sea Water were attributed to sedimentary inputs from the Newfoundland Margin. Bottom waters from the Irminger Sea displayed high DFe concentrations likely due to the dissolution of Fe-rich particles in the Denmark Strait Overflow Water and the Polar Intermediate Water. Finally, the nepheloid layers located in the different basins and at the Iberian Margin were found to act as either a source or a sink of DFe depending on the nature of particles, with organic particles likely releasing DFe and Mn particle scavenging DFe

Dissolved iron in the North Atlantic Ocean and Labrador Sea along the GEOVIDE section (GEOTRACES section GA01)

Abstract. Dissolved Fe (DFe) samples from the GEOVIDE voyage (GEOTRACES GA01, May–June 2014) in the North Atlantic Ocean were analysed using a SeaFAST-picoTM coupled to an Element XR HR-ICP-MS and provided interesting insights on the Fe sources in this area. Overall, DFe concentrations ranged from 0.09 ± 0.01 nmol L−1 to 7.8 ± 0.5 nmol L−1. Elevated DFe concentrations were observed above the Iberian, Greenland and Newfoundland Margins likely due to riverine inputs from the Tagus River, meteoric water inputs and sedimentary inputs. Air-sea interactions were suspected to be responsible for the increase in DFe concentrations within subsurface waters of the Irminger Sea due to deep convection occurring the previous winter, that provided iron-to-nitrate ratios sufficient to sustain phytoplankton growth. Increasing DFe concentrations along the flow path of the Labrador Sea Water were attributed to sedimentary inputs from the Newfoundland Margin. Bottom waters from the Irminger Sea displayed high DFe concentrations likely due to the dissolution of Fe-rich particles from the Denmark Strait Overflow Water and the Polar Intermediate Water. Finally, the nepheloid layers were found to act as either a source or a sink of DFe depending on the nature of particles. </jats:p

Inter-laboratory study for the certification of trace elements in seawater certified reference materials NASS-7 and CASS-6

Certification of trace metals in seawater certified reference materials (CRMs) NASS-7 and CASS-6 is described. At the National Research Council Canada (NRC), column separation was performed to remove the seawater matrix prior to the determination of Cd, Cr, Cu, Fe, Pb, Mn, Mo, Ni, U, V, and Zn, whereas As was directly measured in 10-fold diluted seawater samples, and B was directly measured in 200-fold diluted seawater samples. High-resolution inductively coupled plasma mass spectrometry (HR-ICPMS) was used for elemental analyses, with double isotope dilution for the accurate determination of B, Cd, Cr, Cu, Fe, Pb, Mo, Ni, U, and Zn in seawater NASS-7 and CASS-6, and standard addition calibration for As, Co, Mn, and V. In addition, all analytes were measured using standard addition calibration with triple quadrupole (QQQ)-ICPMS to provide a second set of data at NRC. Expert laboratories worldwide were invited to contribute data to the certification of trace metals in NASS-7 and CASS-6. Various analytical methods were employed by participants including column separation, co-precipitation, and simple dilution coupled to ICPMS detection or flow injection analysis coupled to chemiluminescence detection, with use of double isotope dilution calibration, matrix matching external calibration, and standard addition calibration. Results presented in this study show that majority of laboratories have demonstrated their measurement capabilities for the accurate determination of trace metals in seawater. As a result of this comparison, certified/reference values and associated uncertainties were assigned for 14 elements in seawater CRMs NASS-7 and CASS-6, suitable for the validation of methods used for seawater analysis