The role of humic-type ligands in the bioavailability and stabilization of dissolved iron in the Western Tropical South Pacific Ocean

The high N2 fixation rate observed in the Lau Basin of the western tropical South Pacific Ocean (WTSP) is fueled by iron (Fe) released from shallow hydrothermal systems. Understanding Fe bioavailability is crucial but the controls on the stability and bioavailability of hydrothermal Fe inputs are st...

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Main Authors: Gabriel Dulaquais, Pierre Fourrier, Cécile Guieu, Léo Mahieu, Ricardo Riso, Pascal Salaun, Chloé Tilliette, Hannah Whitby
Format: Article
Language:English
Published: Frontiers Media S.A. 2023-08-01
Series:Frontiers in Marine Science
Subjects:
Online Access:https://www.frontiersin.org/articles/10.3389/fmars.2023.1219594/full
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author Gabriel Dulaquais
Pierre Fourrier
Cécile Guieu
Léo Mahieu
Ricardo Riso
Pascal Salaun
Chloé Tilliette
Hannah Whitby
author_facet Gabriel Dulaquais
Pierre Fourrier
Cécile Guieu
Léo Mahieu
Ricardo Riso
Pascal Salaun
Chloé Tilliette
Hannah Whitby
author_sort Gabriel Dulaquais
collection DOAJ
description The high N2 fixation rate observed in the Lau Basin of the western tropical South Pacific Ocean (WTSP) is fueled by iron (Fe) released from shallow hydrothermal systems. Understanding Fe bioavailability is crucial but the controls on the stability and bioavailability of hydrothermal Fe inputs are still poorly understood. Here, we provide new data on the spatial and vertical distribution of the soluble ubiquitous humic-like ligands (LFeHS) and their associated dissolved Fe (DFe) in the WTSP, including in samples near hydrothermal vents. Our data show that LFeHS are heterogenous ligands with binding sites of both strong and intermediate strengths. These ligands are primarily produced in surface waters and partially mineralized in mesopelagic waters. A substantial fraction of DFe was complexed by LFeHS (mean ~30%). The DFe complexed by LFeHS is likely bioavailable to phytoplankton and LFeHS stabilized Fe released by the mineralization of sinking biomass. However, unsaturation of LFeHS by Fe suggest that part of DFe is not available for complexation with LFeHS. Possible reasons are competition between DFe and other metals, such as dissolved copper, or the inability of LFeHS to access colloidal DFe. The study of two volcanic sites indicates that LFeHS were not produced in these hydrothermal systems. At the active site (DFe ~50 nmol L-1), LFeHS can only partially solubilize the hydrothermal DFe released in this area (1~5.5% of the total DFe). We performed controlled laboratory experiments which show that the observed low solubilization yield result from the inability of LFeHS to solubilize aged Fe oxyhydroxides (FeOx - a kinetically mediated process) and to form stable complexes with Fe(II) species. Our study provides new understanding of the role of LFeHS on the bioavailability and stabilization of hydrothermal DFe.
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spelling doaj.art-1df1ff3f328843619e8dcd7fa4d862a02023-08-21T14:17:39ZengFrontiers Media S.A.Frontiers in Marine Science2296-77452023-08-011010.3389/fmars.2023.12195941219594The role of humic-type ligands in the bioavailability and stabilization of dissolved iron in the Western Tropical South Pacific OceanGabriel Dulaquais0Pierre Fourrier1Cécile Guieu2Léo Mahieu3Ricardo Riso4Pascal Salaun5Chloé Tilliette6Hannah Whitby7Laboratoire des Sciences de l’Environnement Marin Centre nationale pour la recherche scientifiques (CNRS) UMR 6539, Institut Universitaire Européen de la Mer, Université de Bretagne Occidentale, Plouzané, FranceLaboratoire des Sciences de l’Environnement Marin Centre nationale pour la recherche scientifiques (CNRS) UMR 6539, Institut Universitaire Européen de la Mer, Université de Bretagne Occidentale, Plouzané, FranceSorbonne Université, Centre nationale pour la recherche scientifiques (CNRS), Laboratoire d’Océanographie de Villefranche (LOV), Villefranche‐sur‐Mer, FranceDepartment of Earth, Ocean and Ecological Sciences, School of Environmental Sciences, University of Liverpool, United KingdomLaboratoire des Sciences de l’Environnement Marin Centre nationale pour la recherche scientifiques (CNRS) UMR 6539, Institut Universitaire Européen de la Mer, Université de Bretagne Occidentale, Plouzané, FranceDepartment of Earth, Ocean and Ecological Sciences, School of Environmental Sciences, University of Liverpool, United KingdomSorbonne Université, Centre nationale pour la recherche scientifiques (CNRS), Laboratoire d’Océanographie de Villefranche (LOV), Villefranche‐sur‐Mer, FranceDepartment of Earth, Ocean and Ecological Sciences, School of Environmental Sciences, University of Liverpool, United KingdomThe high N2 fixation rate observed in the Lau Basin of the western tropical South Pacific Ocean (WTSP) is fueled by iron (Fe) released from shallow hydrothermal systems. Understanding Fe bioavailability is crucial but the controls on the stability and bioavailability of hydrothermal Fe inputs are still poorly understood. Here, we provide new data on the spatial and vertical distribution of the soluble ubiquitous humic-like ligands (LFeHS) and their associated dissolved Fe (DFe) in the WTSP, including in samples near hydrothermal vents. Our data show that LFeHS are heterogenous ligands with binding sites of both strong and intermediate strengths. These ligands are primarily produced in surface waters and partially mineralized in mesopelagic waters. A substantial fraction of DFe was complexed by LFeHS (mean ~30%). The DFe complexed by LFeHS is likely bioavailable to phytoplankton and LFeHS stabilized Fe released by the mineralization of sinking biomass. However, unsaturation of LFeHS by Fe suggest that part of DFe is not available for complexation with LFeHS. Possible reasons are competition between DFe and other metals, such as dissolved copper, or the inability of LFeHS to access colloidal DFe. The study of two volcanic sites indicates that LFeHS were not produced in these hydrothermal systems. At the active site (DFe ~50 nmol L-1), LFeHS can only partially solubilize the hydrothermal DFe released in this area (1~5.5% of the total DFe). We performed controlled laboratory experiments which show that the observed low solubilization yield result from the inability of LFeHS to solubilize aged Fe oxyhydroxides (FeOx - a kinetically mediated process) and to form stable complexes with Fe(II) species. Our study provides new understanding of the role of LFeHS on the bioavailability and stabilization of hydrothermal DFe.https://www.frontiersin.org/articles/10.3389/fmars.2023.1219594/fullironorganic complexationhumic substanceshydrothermal ventsPacific Ocean
spellingShingle Gabriel Dulaquais
Pierre Fourrier
Cécile Guieu
Léo Mahieu
Ricardo Riso
Pascal Salaun
Chloé Tilliette
Hannah Whitby
The role of humic-type ligands in the bioavailability and stabilization of dissolved iron in the Western Tropical South Pacific Ocean
Frontiers in Marine Science
iron
organic complexation
humic substances
hydrothermal vents
Pacific Ocean
title The role of humic-type ligands in the bioavailability and stabilization of dissolved iron in the Western Tropical South Pacific Ocean
title_full The role of humic-type ligands in the bioavailability and stabilization of dissolved iron in the Western Tropical South Pacific Ocean
title_fullStr The role of humic-type ligands in the bioavailability and stabilization of dissolved iron in the Western Tropical South Pacific Ocean
title_full_unstemmed The role of humic-type ligands in the bioavailability and stabilization of dissolved iron in the Western Tropical South Pacific Ocean
title_short The role of humic-type ligands in the bioavailability and stabilization of dissolved iron in the Western Tropical South Pacific Ocean
title_sort role of humic type ligands in the bioavailability and stabilization of dissolved iron in the western tropical south pacific ocean
topic iron
organic complexation
humic substances
hydrothermal vents
Pacific Ocean
url https://www.frontiersin.org/articles/10.3389/fmars.2023.1219594/full
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