A call for refining the role of humic-like substances in the oceanic iron cycle

Primary production by phytoplankton represents a major pathway whereby atmospheric CO2 is sequestered in the ocean, but this requires iron, which is in scarce supply. As over 99% of iron is complexed to organic ligands, which increase iron solubility and microbial availability, understanding the processes governing ligand dynamics is of fundamental importance. Ligands within humic-like substances have long been considered important for iron complexation, but their role has never been explained in an oceanographically consistent manner. Here we show iron co-varying with electroactive humic substances at multiple open ocean sites, with the ratio of iron to humics increasing with depth. Our results agree with humic ligands composing a large fraction of the iron-binding ligand pool throughout the water column. We demonstrate how maximum dissolved iron concentrations could be limited by the concentration and binding capacity of humic ligands, and provide a summary of the key processes that could influence these parameters. If this relationship is globally representative, humics could impose a concentration threshold that buffers the deep ocean iron inventory. This study highlights the dearth of humic data, and the immediate need to measure electroactive humics, dissolved iron and iron-binding ligands simultaneously from surface to depth, across different ocean basins

Freshwater exports from Arctic to the Labrador and Greenland shelf andslope.

Publisher's version (útgefin grein)We investigate whether one can detect changes in the freshwater contributions to the North Atlantic subpolar gyre(SPG), in light of the observed recent decrease of salinity in the region. We focus on two important conduits offreshwater from the Arctic to the interior North Atlantic subpolar gyre: the Coastal Labrador Current and thesouthern Greenland shelf, and use a dataset of different freshwater tracers from a set of cruises over the period2010-2014.Icelandic research institute (RANNÍS no. 152229)Peer reviewe

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

Measurement of the isotopic composition of dissolved iron in the open ocean

This work demonstrates for the first time the feasibility of the measurement of the isotopic composition of dissolved iron in seawater for a typical open ocean Fe concentration range (0.1-1 nM). It also presents the first data of this kind. Iron is preconcentrated using a Nitriloacetic Acid Superflow resin and purified using an AG1x4 anion exchange resin. The isotopic ratios are measured with a MC-ICPMS Neptune, coupled with a desolvator (Aridus II), using a Fe-57-Fe-58 double spike mass bias correction. Measurement precision (0.13%, 2SD) allows resolving small iron isotopic composition variations within the water column, in the Atlantic sector of the Southern Ocean (from delta Fe-57 = -0.19 to +0.32 parts per thousand). Isotopically light iron found in the Upper Circumpolar Deep Water is hypothesized to result from organic matter remineralization. Shallow samples suggest that, if occurring, an iron isotopic fractionation during iron uptake by phytoplankton is characterized by a fractionation factor, such as: vertical bar Delta Fe-57((plankton-seawater))vertical bar < 0.48 parts per thousand

The unaccounted dissolved iron (II) sink: Insights from dFe(II) concentrations in the deep Atlantic Ocean

Hydrothermal vent sites found along mid-ocean ridges are sources of numerous reduced chemical species and trace elements. To establish dissolved iron (II) (dFe(II)) variability along the Mid Atlantic Ridge (between 39.5°N and 26°N), dFe(II) concentrations were measured above six hydrothermal vent sites, as well as at stations with no active hydrothermal activity. The dFe(II) concentrations ranged from 0.00 to 0.12 nmol L-1 (detection limit = 0.02 ± 0.02 nmol L-1) in non-hydrothermally affected regions to values as high as 12.8 nmol L-1 within hydrothermal plumes. Iron (II) in seawater is oxidised over a period of minutes to hours, which is on average two times faster than the time required to collect the sample from the deep ocean and its analysis in the onboard laboratory. A multiparametric equation was used to estimate the original dFe(II) concentration in the deep ocean. The in-situ temperature, pH, salinity and delay between sample collection and its analysis were considered. The results showed that dFe(II) plays a more significant role in the iron pool than previously accounted for, constituting a fraction >20 % of the dissolved iron pool, in contrast to <10 % of the iron pool formerly reported. This discrepancy is caused by Fe(II) loss during sampling when between 35 and 90 % of the dFe(II) gets oxidised. In-situ dFe(II) concentrations are therefore significantly higher than values reported in sedimentary and hydrothermal settings where Fe is added to the ocean in its reduced form. Consequently, the high dynamism of dFe(II) in hydrothermal environments masks the magnitude of dFe(II) sourced within the deep ocean

The unaccounted dissolved iron (II) sink: Insights from dFe(II) concentrations in the deep Atlantic Ocean

Hydrothermal vent sites found along mid-ocean ridges are sources of numerous reduced chemical species and trace elements. To establish dissolved iron (II) (dFe(II)) variability along the Mid Atlantic Ridge (between 39.5°N and 26°N), dFe(II) concentrations were measured above six hydrothermal vent sites, as well as at stations with no active hydrothermal activity. The dFe(II) concentrations ranged from 0.00 to 0.12 nmol L−1 (detection limit = 0.02 ± 0.02 nmol L−1) in non-hydrothermally affected regions to values as high as 12.8 nmol L−1 within hydrothermal plumes. Iron (II) in seawater is oxidised over a period of minutes to hours, which is on average two times faster than the time required to collect the sample from the deep ocean and its analysis in the onboard laboratory. A multiparametric equation was used to estimate the original dFe(II) concentration in the deep ocean. The in-situ temperature, pH, salinity and delay between sample collection and its analysis were considered. The results showed that dFe(II) plays a more significant role in the iron pool than previously accounted for, constituting a fraction >20 % of the dissolved iron pool, in contrast to <10 % of the iron pool formerly reported. This discrepancy is caused by Fe(II) loss during sampling when between 35 and 90 % of the dFe(II) gets oxidised. In-situ dFe(II) concentrations are therefore significantly higher than values reported in sedimentary and hydrothermal settings where Fe is added to the ocean in its reduced form. Consequently, the high dynamism of dFe(II) in hydrothermal environments masks the magnitude of dFe(II) sourced within the deep ocean

Net and gross incorporation of nitrogen by marine copepods fed on 15N-labelled diatoms: Methodology and trophic studies

International audienc

Pervasive sources of isotopically light zinc in the North Atlantic Ocean

In this study, we report seawater dissolved zinc (Zn) concentration and isotope composition (Zn) from the GEOTRACES GA01 (GEOVIDE) section in the North Atlantic. Across the transect, three subsets of samples stand out due to their isotopically light signature: those close to the Reykjanes Ridge, those close to the sediments, and those, pervasively, in the upper ocean. Similar to observations at other locations, the hydrothermal vent of the Reykjanes Ridge is responsible for the isotopically light Zn composition of the surrounding waters, with an estimated source Zn of -0.42 ‰. This isotopically light Zn is then transported over a distance greater than 1000 km from the vent. Sedimentary inputs are also evident all across the trans-Atlantic section, highlighting a much more pervasive process than previously thought. These inputs of isotopically light Zn, ranging from -0.51 to +0.01 ‰, may be caused by diffusion out of Zn-rich pore waters, or by dissolution of sedimentary particles. The upper North Atlantic is dominated by low Zn, a feature that has been observed in all Zn isotope datasets north of the Southern Ocean. Using macronutrient to Zn ratios to better understand modifications of preformed signatures exported from the Southern Ocean, we suggest that low upper-ocean Zn results from addition of isotopically light Zn to the upper ocean, and not necessarily from removal of heavy Zn through scavenging. Though the precise source of this isotopically light upper-ocean Zn is not fully resolved, it seems possible that it is anthropogenic in origin. This view of the controls on upper-ocean Zn is fundamentally different from those put forward previously

Inputs and processes affecting the distribution of particulate iron in the North Atlantic along the GEOVIDE (GEOTRACES GA01) section

The GEOVIDE cruise (May–June 2014, R/V Pourquoi Pas?) aimed to provide a better understanding on trace metal biogeochemical cycles in the North Atlantic. As particles play a key role in the global biogeochemical cycle of trace elements in the ocean, we discuss the distribution of particulate iron (PFe), in light of particulate aluminium (PAl), manganese (PMn) and phosphorus (PP) distributions. Overall, 32 full vertical profiles were collected for trace metal analyses, representing more than 500 samples. This resolution provides a solid basis for assessing concentration distributions, elemental ratios, size-fractionation, or adsorptive scavenging processes in key areas of the thermohaline circulation. Total particulate iron (PFe) concentrations ranged from as low as 9 pmol L−1 in surface Labrador Sea waters to 304 nmol L−1 near the Iberian margin, while median PFe concentrations of 1.15 nmol L−1 were measured over the sub-euphotic ocean interior. At most stations over the Western, the relative concentrations of total PFe and aluminium (PAl) showed the near-ubiquitous influence of crustal particles in the water column. Overall, the lithogenic component explained more than 87 % of PFe variance along the section. Within the Irminger and Labrador basins, the formation of biogenic particles led to an increase of the PFe / PAl ratio (up to 0.7 mol mol−1) compared to the continental crust ratio (0.21 mol mol−1), Margins provide important quantities of particulate trace elements (up to 10 nmol L−1 of PFe) to the open ocean, and in the case of the Iberian margin, advection of PFe was visible more than 250 km away from the margin. Additionally, several benthic nepheloid layers spreading over 200m above the seafloor were encountered along the transect, especially in the Icelandic, Irminger and Labrador basins, delivering particles with high PFe content, up to 89 nmol L−1 of PFe. Finally, remineralisation processes are also discussed, and showed different patterns among basins and elements

Particulate Trace Element Export in the North Atlantic (GEOTRACES GA01 Transect, GEOVIDE Cruise)

Vertical export of particulate trace elements (pTEs) is a critically underconstrained aspect of their biogeochemistry. Here, we combine elemental analyses on large (>53 μm) particles and 234Th measurements to determine downward export fluxes from the upper layers (40–110 m) of pTEs (Al, Cd, Co, Cu, Fe, Mn, Ni, P, Ti, V, Zn) and mineral phases (lithogenic, Fe- and Mn-oxides, calcium carbonate, and opal) in the North Atlantic along the GEOVIDE transect (Portugal–Greenland–Canada; GEOTRACES GA01 cruise). The role of lithogenic particles in controlling TE fluxes is obvious at proximity of the Iberian margin where the highest pTE export fluxes were estimated (up to 3912 μg/m2/d for pFe). However, high lithogenic and pTE fluxes are also observed up to 1700 km off this margin in the west European and Icelandic basins (up to 931 μg/m2/d for pFe). The lowest pTE export fluxes are determined in the Labrador Sea (as low as 501 μg/m2/d for pFe). High Mn- and Fe-oxide fluxes are estimated at the open ocean stations, suggesting that authigenic particles are an important vector of pTEs. All along the transect, biogenic particles also drive the pTE export fluxes, as shown by the similar pTE/POC ratios between exports and phytoplankton quotas. The shortest residence times (dissolved + particulate) are generally observed where lithogenic particles control the pTE fluxes (as low as 2 days for Fe) whereas pTEs seem to be longer retained when the contribution of biogenic particles become greater (residence times up to 147 days for Fe)