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

Iron complexation by phenolic ligands in seawater

International audienceIron is an essential micronutrient for phytoplankton and can limit primary production in the ocean. Fe chemistry is highly controlled by its interaction with organic complexes (> 99%). It is still unknown which organic compounds produced by cells have the ability to bind Fe. Within the pool of organic ligands, polyphenols are known to be exudated by marine diatoms and, in this study, the role of three polyphenols ((+/-) - catechin, sinapic acid and gallic acid) was studied in terms of dissolved Fe complexation via kinetic and titration approaches, and also their role as a source of Fe(II) in seawater. The results demonstrated that these three polyphenols are weak L-2-type Fe-binding ligands according to the conditional stability constant, computed by using the kinetic approach (log K'(Fe'L)= 8.86-9.2), where the formation rate constant (k(f)) was 3.1.10(5)-4.2.10(5) M-1 s(-1) and the dissociation rate constant (k(d)) was 2.43.10(-4)-4.4.10(-4) s(-1). The conditional stability was also computed from the titration approach with log K'(Fe'L) from 8.6 to 9.5. These studied ligands also regenerated Fe(II) in seawater from 0.05% to 11.92%. The results obtained in this study suggest that polyphenols increase the persistence of dissolved Fe and should be considered as an important Fe-binding ligands in seawater to better understand the global biogeochemical cycles.This article is part of a special issue entitled: "Cycles of trace elements and isotopes in the ocean - GEOTRACES and beyond" - edited by Tim M. Conway, Tristan Horner, Yves Plancherel, and Aridane G. Gonzalez

State of rare earth elements in the sediment and their bioaccumulation by mangroves: a case study in pristine islands of Indian Sundarban

WOS:000464851100069International audienceThe mangrove ecosystems are known to efficiently sequester trace metals both in sediments and plant biomass. However, less is known about the chemistry of rare earth elements (REE) in the coastal environments, especially in the world's largest mangrove province, the Sundarban. Here, the concentration of REE in the sediment and plant organs of eight dominant mangrove species (mainly Avicennia sp.) in the Indian Sundarban was measured to assess REE sources, distribution, and bioaccumulation state. Results revealed that light REE (LREE) were more concentrated than the heavy REE (HREE) (128-144 mg kg(-1) and 12-15 mg kg(-1), respectively) in the mangrove sediments, with a relatively weak positive europium anomaly (Eu/Eu* = 1.03-1.14) with respect to North American shale composite. The primary source of REE was most likely linked to aluminosilicate weathering of crustal materials, and the resultant increase in LREE in the detritus. Vertical distribution of REE in one of the long cores from Lothian Island was altered by mangrove root activity and dependent on various physicochemical properties in the sediment (e.g., Eh, pH, organic carbon, and phosphate). REE uptake by plants was higher in the below-ground parts than in the above-ground plant tissues (root = 3.3 mg kg(-1), leaf + wood = 1.7 mg kg(-1)); however, their total concentration was much lower than in the sediment (149.5 mg kg(-1)). Species-specific variability in bioaccumulation factor and translocation factor was observed indicating different REE partitioning and varying degree of mangrove uptake efficiency. Total REE stock in plant (above + live below ground) was estimated to be 168 g ha(-1) with LREE contributing similar to 90% of the stock. This study highlighted the efficiency of using REE as a biological proxy in determining the degree of bioaccumulation within the mangrove environment

Accumulation, transport and toxicity of arsenic in the Sundarbans mangrove, India

International audienceArsenic (As), a toxic element is a concern for the habitants in and around the coastal areas of West Bengal (India) where world's largest Sundarbans mangrove is situated. Little is known about the potential of these mangroves in storing As within their biomass and transporting to the Bay of Bengal. A comprehensive yearly data of above ground and below ground biomass (AGB, BGB), and exchange fluxes like litter fall, plant uptake, sedimentary diffusion/advection, and suspended particle deposition were used in a box model for constructing As budget for the Sundarbans mangroves. About 80% of total As was stored in AGB while As stock in sediment was several hundred times higher than in the AGB and BGB indicating poor bioaccumulation and sequestration capacity of the mangroves, which was further supported by higher As loss though litterfall (16.8 mu g As m(-2) month(-1)) compared to gain through plant uptake (0.05 mu g As m(-2) month(-)(1)). About 65% of the river-discharged As exported to the Bay of Bengal, the rest amounting to 67.2 x 10(3) kg yr(-1) remained in the mangrove estuaries. Although ecotoxicological indexes confirmed low As pollution impact in the Sundarbans, mass budget revealed net As addition in the estuarine ecosystem (67.2 Mg As yr(-1)), mainly derived from natural and anthropogenic sources such as, contamination via atmospheric dust deposition. Overall reservoir-based mass budget showed weak As sequestration capacity by these mangroves. The approach developed for As in this study could be applied to other major metals to estimate metal sequestration and conservation potential by the Sundarbans mangroves

Ocean alkalinity enhancement using sodium carbonate salts does not lead to measurable changes in Fe dynamics in a mesocosm experiment

The addition of carbonate minerals to seawater through an artificial ocean alkalinity enhancement (OAE) process increases the concentrations of hydroxide, bicarbonate, and carbonate ions. This leads to changes in the pH and the buffering capacity of the seawater. Consequently, OAE could have relevant effects on marine organisms and in the speciation and concentration of trace metals that are essential for their physiology. During September and October 2021, a mesocosm experiment was carried out in the coastal waters of Gran Canaria (Spain), consisting on the controlled variation of total alkalinity (TA). Different concentrations of carbonate salts (NaHCO3 and Na2CO3) previously homogenized were added to each mesocosm to achieve an alkalinity gradient between Δ0 to Δ2400 µmol L−1. The lowest point of the gradient was 2400 µmol kg−1, being the natural alkalinity of the medium, and the highest point was 4800 µmol kg−1. Iron (Fe) speciation was monitored during this experiment to analyse total dissolved iron (TdFe, unfiltered samples), dissolved iron (dFe, filtered through a 0.2 µm pore size filter), soluble iron (sFe, filtered through a 0.02 µm pore size filter), dissolved labile iron (dFe′), iron-binding ligands (LFe), and their conditional stability constants () because of change due to OAE and the experimental conditions in each mesocosm. Observed iron concentrations were within the expected range for coastal waters, with no significant increases due to OAE. However, there were variations in Fe size fractionation during the experiment. This could potentially be due to chemical changes caused by OAE, but such an effect is masked by the stronger biological interactions. In terms of size fractionation, sFe was below 1.0 nmol L−1, dFe concentrations were within 0.5–4.0 nmol L−1, and TdFe was within 1.5–7.5 nmol L−1. Our results show that over 99 % of Fe was complexed, mainly by L1 and L2 ligands with ranging between 10.92 ± 0.11 and 12.68 ± 0.32, with LFe ranging from 1.51 ± 0.18 to 12.3 ± 1.8 nmol L−1. Our data on iron size fractionation, concentration, and iron-binding ligands substantiate that the introduction of sodium salts in this mesocosm experiment did not modify iron dynamics. As a consequence, phytoplankton remained unaffected by alterations in this crucial element

Metal and proton adsorption capacities of natural and cloned Sphagnum mosses

Terrestrial mosses are commonly used as bioindicators of atmospheric pollution. However, there is a lack of standardization of the biomonitoring preparation technique and the efficiency of metal adsorption by various moss species is poorly known. This is especially true for in vitro-cultivated moss clones, which are promising candidates for a standardized moss-bag technique. We studied the adsorption of copper and zinc on naturally grown Sphagnum peat moss in comparison with in vitro-cultivated Sphagnum palustre samples in order to provide their physico-chemical characterization and to test the possibility of using cloned peat mosses as bioindicators within the protocol of moss-bag technique. We demonstrate that in vitro-grown clones of S. palustre exhibit acid–base properties similar to those of naturally grown Sphagnum samples, whereas the zinc adsorption capacity of the clones is approx. twice higher than that of the samples from the field. At the same time, the field samples adsorbed 30–50% higher amount of Cu2+ compared to that of the clones. This contrast may be related to fine differences in the bulk chemical composition, specific surface area, morphological features, type and abundance of binding sites at the cell surfaces and in the aqueous solution of natural and cloned Sphagnum. The clones exhibited much lower concentration of most metal pollutants in their tissues relative to the natural samples thus making the former better indicators of low metal loading. Overall, in vitro-produced clones of S. palustre can be considered as an adequate, environmentally benign substitution for protected natural Sphagnum sp. samples to be used in moss-bags for atmospheric monitorin

Metal and proton adsorption capacities of natural and cloned Sphagnum mosses

Terrestrial mosses are commonly used as bioindicators of atmospheric pollution. However, there is a lack of standardization of the biomonitoring preparation technique and the efficiency of metal adsorption by various moss species is poorly known. This is especially true for in vitro-cultivated moss clones, which are promising candidates for a standardized moss-bag technique. We studied the adsorption of copper and zinc on naturally grown Sphagnum peat moss in comparison with in vitro-cultivated Sphagnum palustre samples in order to provide their physico-chemical characterization and to test the possibility of using cloned peat mosses as bioindicators within the protocol of moss-bag technique. We demonstrate that in vitro-grown clones of S. palustre exhibit acid–base properties similar to those of naturally grown Sphagnum samples, whereas the zinc adsorption capacity of the clones is approx. twice higher than that of the samples from the field. At the same time, the field samples adsorbed 30–50% higher amount of Cu2+ compared to that of the clones. This contrast may be related to fine differences in the bulk chemical composition, specific surface area, morphological features, type and abundance of binding sites at the cell surfaces and in the aqueous solution of natural and cloned Sphagnum. The clones exhibited much lower concentration of most metal pollutants in their tissues relative to the natural samples thus making the former better indicators of low metal loading. Overall, in vitro-produced clones of S. palustre can be considered as an adequate, environmentally benign substitution for protected natural Sphagnum sp. samples to be used in moss-bags for atmospheric monitorin

Revisiting the distribution of oceanic N2 fixation and estimating diazotrophic contribution to marine production

The geographical distribution and controlling factors of marine N2 fixation are understudied. Here the authors find increasing rates of N2 fixation from the Sargasso Sea to the coastal waters of North America, driven primarily by cyanobacterial diazotrophs and best correlated with phosphorus availability and chlorophyll-a concentrations

Interactive Impacts of Silver and Phosphorus on Autotrophic Biofilm Elemental and Biochemical Quality for a Macroinvertebrate Consumer

International audienc