Evidence for the production of copper-complexing ligands by marine phytoplankton in the subarctic northeast Pacific

Nixon, Richard L.; Peña, M. Angélica; Taves, Robyn; Janssen, David J.; Cullen, Jay T.; Ross, Andrew R. S.

doi:10.1016/j.marchem.2021.104034

Cited by 4 publications

(4 citation statements)

References 66 publications

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“…This work found that the extracted Cu compounds contained nitrogen and thiollike functional groups, and were similar to some ligands that had been found in algal cultures. Cu-binding ligands identified using Cu(II)-IMAC in the northeast Pacific along Line P also correlated with chlorophyll a and phaeopigments across both near shore and offshore stations and in different seasons, providing additional evidence for a biological ligand source 98 . Voltammetric studies have also routinely noted high ligand concentrations and low dissolved Cu concentrations in surface waters and in the chlorophyll maximum 8,16,103 .…”

Section: Anodic Stripping Voltammetry (Asv)mentioning

confidence: 81%

“…This method is promising in that it is able to isolate only Cu-binding ligands while other solid phase extraction techniques capture a myriad of organic compounds. Both the Cu(II)-IMAC method and the mass spectrometry methods that have been employed thus far to identify and characterize the organic Cu-binding ligand pool in seawater have the potential to rapidly accelerate our understanding of marine Cu complexation, but very few published studies exist [95][96][97][98][99] . Importantly, new work also suggests that a large fraction of dissolved Cu (up to 90%) in deep waters may be inert, which has implications for these analytical methods as well as for dissolved Cu reactivity and bioavailability 91 .…”

Section: Anodic Stripping Voltammetry (Asv)mentioning

confidence: 99%

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Sources, sinks, and cycling of dissolved organic copper binding ligands in the ocean

Ruacho

Richon²,

Whitby³

et al. 2022

Commun Earth Environ

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Organic Cu-binding ligands have a fundamental influence on Cu distributions in the global ocean and they complex >99% of the dissolved Cu in seawater. Cu-binding ligands however, represent a large diversity of compounds with distinct sources, sinks and chemical properties. This heterogeneity makes the organic Cu-binding ligand pool difficult to study at the global scale. In this review, we provide an overview of the diversity of compounds that compose the marine Cu-ligand pool, and their dominant sources and sinks. We also summarize the most common analytical methods to measure ligands in marine water column samples. Generally, ligands are classified according to their conditional binding strength to Cu. However, the lack of a common definition for Cu ligand categories has previously complicated data intercomparison. To address this, we provide a general classification for Cu-binding ligands according to their binding strength and discuss emerging patterns in organic Cu-binding ligand distributions in the ocean according to this classification. To date, there is no global biogeochemical model that explicitly represents Cu ligands. We provide estimates of organic Cu-binding ligand fluxes at key interfaces as first order estimates and a first step for future modeling efforts focused on Cu and Cu-binding ligands.

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Section: Anodic Stripping Voltammetry (Asv)mentioning

confidence: 81%

Section: Anodic Stripping Voltammetry (Asv)mentioning

confidence: 99%

Sources, sinks, and cycling of dissolved organic copper binding ligands in the ocean

Ruacho

Richon²,

Whitby³

et al. 2022

Commun Earth Environ

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“…More recently, copper speciation has also been measured in the Arctic (Arnone et al, 2023(Arnone et al, , 2024. Methods complementary to CLE-AdCSV have provided further information on copper lability (Moriyasu and Moffett, 2022;Moriyasu et al, 2023), and have allowed us to interrogate ligand sources (Karavoltsos et al, 2013;Nixon et al, 2019Nixon et al, , 2021 as well as to study the uptake of ligand-bound copper (Semeniuk et al, 2015). Copperbinding ligands (along with those for nickel) have also been characterized at the molecular level (Boiteau et al, 2016b;Babcock-Adams, 2022).…”

Section: Spatial Distribution Of Metal-binding Ligandsmentioning

confidence: 99%

New Insights into the Organic Complexation of Bioactive Trace Metals in the Global Ocean from the GEOTRACES Era

Whitby,

Park,

Shaked

et al. 2024

Oceanog

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The GEOTRACES program has greatly expanded measurements of dissolved trace metal concentrations across ocean basins, but to understand the behavior and cycling of metals and their impacts on primary productivity, we must understand the chemical forms in which they are present in the environment. Organic ligands play a central role in the speciation and cycling of trace metals in the marine environment, controlling their chemical reactivity and bioavailability. Here, we present an overview of the contributions the GEOTRACES program has made to understanding ocean metal speciation through advancing our knowledge of the distribution, sources, and sinks of metal-binding organic ligands across the global ocean, particularly for iron. Detailed assessments and intercalibration of the speciation methods most commonly applied have allowed integration of metal-binding ligand measurements across datasets. Work to characterize specific ligand groups within the wider pool of dissolved organic matter, along with their sources and sinks, is starting to unravel the role of metal-binding organic ligands in global biogeochemical cycles. Recent advances in complementary analytical techniques using liquid chromatography and mass spectrometry present a molecular picture of metal speciation and bioavailability—and also pose new questions. Moving forward, we need to address knowledge gaps in our understanding of how metal speciation and complexation relates to bioavailability in order to recognize the impacts of ocean metal distributions and cycling on marine productivity and the global carbon cycle.

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“…Regarding diatom genera, the most abundant were Chaetoceros (35.1%) and Leptocylindrus (15.2%), followed by Cylindrotheca and Pseudonitzschia (approximately 14% each), with the rest of the genera detected at frequencies lower than 5% (Figure 8). Marine phytoplankton constitutes a significant source of copper ligands (Thompson et al, 2014;Nixon et al, 2019), with the fluctuations of ligand concentrations observed close to the sea surface being associated with phytoplankton ecology alterations (Nixon et al, 2021). Emiliania huxleyi coccolithophore produces a combination of low concentrations of strong Cu ligands with high concentrations of weak Cu ligands (Leal et al, 1999;Croot et al, 2000;Echeveste et al, 2018) and Thalassiosira weissflogii diatom phytochelatins as Cd complexing agents (Lee et al, 1996).…”

Section: Sources Of Metal Ligandsmentioning

confidence: 99%

Metal complexation, FT-IR characterization, and plankton abundance in the marine surface microlayer of coastal areas in the Eastern Mediterranean

et al. 2022

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Barely any data exist on metal speciation in the marine surface microlayer (SML), a rather complex environment, the study of which contributes to enhancement of knowledge on metal speciation and its effect to the ocean. Metal speciation is significant since life requires a wide variety of trace metals that are essential for the growth of the organisms. Ligand concentrations (L) of copper (Cu), zinc (Zn), and cadmium (Cd) were studied by anodic stripping voltammetry (ASV) in the SML of coastal areas within the Aegean Sea in the Eastern Mediterranean. Complexing capacities in the SML in decreasing order ranged for Cu from 29 to 201 nM (median 101 nM), for Zn 24–149 nM (45 nM), and for Cd 1.0–1.5 nM (1.4 nM). Average enrichment factors (EFs) of SML samples compared to subsurface ones (SSW) were calculated equal to 0.9 ± 0.8, 1.2 ± 0.5, and 1.7 ± 1.6 for LZn, LCu, and LCd, respectively. In five out of the six total paired samples of SML and SSW, lower concentrations of LZn were measured in the SML, which is not the case for LCu and LCd. Due to elevated dissolved Zn concentrations in the SML, its complexation is incomplete, contrary to those of Cu and Cd, which are fully complexed. These trace metals are essential nutrients for biological functions, hence any differences on their concentration and chemical speciation may directly influence the distribution of phytoplankton species in the upper water column and neuston. EFs of SML relatively to subsurface water ranged in average between 1.2 and 2.4 for total organic carbon (TOC), chlorophyll a (Chla), and plankton, being generally >2 for most of the amino acids detected, demonstrating a relative enrichment of the SML in organic matter. A significant correlation was found between Cu ligands and dinoflagellates <20 μm, confirming older findings supporting that marine dinoflagellates of Gymnodinium genera produce Cu ligands. New insights are provided in the study and the importance of investigating bio-essential metal ions (Cu, Zn, Cd) and their organic complexes in the SML is pointed. Data on Zn and Cd complexing capacities in the SML are the first published so far.

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Evidence for the production of copper-complexing ligands by marine phytoplankton in the subarctic northeast Pacific

Cited by 4 publications

References 66 publications

Sources, sinks, and cycling of dissolved organic copper binding ligands in the ocean

Sources, sinks, and cycling of dissolved organic copper binding ligands in the ocean

New Insights into the Organic Complexation of Bioactive Trace Metals in the Global Ocean from the GEOTRACES Era

Metal complexation, FT-IR characterization, and plankton abundance in the marine surface microlayer of coastal areas in the Eastern Mediterranean

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