the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Organic iron-binding ligands mediate dissolved-particulate exchange in hydrothermal vent plumes along the mid-Atlantic Ridge
Abstract. Hydrothermal vents are important contributors to the dissolved iron inventory in the ocean. Investigating the processes underlying iron behavior in hydrothermal plumes is challenging, but important for constraining deep ocean iron cycling. Field studies suggest that the retention of hydrothermal iron in the deep ocean is primarily supported by two mechanisms: the formation of colloidal nanoparticles and the stabilization of iron by organic ligands. Here we present a novel dataset from shipboard incubation experiments designed to investigate the interplay between these two processes and how they contribute to the stabilization of iron away from ridge axes. Filtered and unfiltered water collected from the hydrothermal plumes of three vent fields along the Mid-Atlantic Ridge as part of GEOTRACES cruise GA13 was incubated in the dark and regularly sampled over time (up to 3 weeks) for concentrations of size-fractionated iron and iron-binding ligands, for dissolved iron isotopic composition, and for microbial community composition. We observed rapid exchange of iron between physiochemical phases that appeared to be mediated in part by organic iron-binding ligands at each stage of plume evolution. Weaker iron-binding ligands sources from the vents were largely lost to the particulate phase with colloidal Fe phases via aggregation early in plume development, similar to the loss of iron and organic matter commonly observed in estuarine systems. Soluble organic ligand production was observed in later stages of all unfiltered incubations followed by mobilization of particulate and colloidal Fe into the soluble phase in the longer incubations, revealing a potentially important mechanism for generating the persistent iron observed in long-range plumes.
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RC1: 'Comment on egusphere-2025-1798', Anonymous Referee #1, 15 Jun 2025
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Dear Authors,
This is a novel and insightful study that contributes to our understanding of the biogeochemical cycle of iron, particularly in hydrothermal regions. The manuscript will be supported for publication once the following issues are addressed. I would like to thank the authors this effort to have all the amount of analysis for the paper from that cruise.
Minor Comments:
- Please correct the term "physiochemical" to "physico-chemical" throughout the manuscript.
- Lines 97–102: This information may be omitted from the introduction as it is repeated in the experimental section.
- The introduction should include an overview of existing incubation studies found in the literature.
- Lines 196–198: This sentence is redundant with previous content and could be removed.
Technical Issues:
- The authors should justify the use of two different artificial ligands for LFe determination. Since both reverse and forward titration methods can use the same ligand, this would allow for direct comparison of conditional stability constants, which are ligand-dependent.
Cheize et al. (2012) demonstrated that NN is suitable for low-salinity solutions. However, in this incubation study, samples could be diluted using UV-irradiated seawater or NaCl to maintain constant ionic strength. Altering ionic strength significantly influences physico-chemical processes and iron speciation.Cheize, M., et al. (2012). Iron organic speciation determination in rainwater using cathodic stripping voltammetry. Analytica Chimica Acta, 736, 45–54.
- Please justify the selected detection window with SA and explain why an alternative was not used that might allow the identification of weaker ligands.
- Why is the equilibration time with SA limited to only one hour? Justification is needed, as most studies. including those by van den Berg, typically use overnight equilibration.
- What is the concentration of Fe(II) in the samples? This is important because the voltammetric method used detects only Fe(III). If Fe(II) is present in significant and stable amounts, LFe values could be overestimated.
- In the forward titrations, are the samples diluted? If so, was salinity corrected accordingly?
- How did the pH evolve during the incubations? pH plays a key role in Fe(II) oxidation and associated physico-chemical processes.
- In Figures 2c and 2e, dFe (and consequently dLFe) concentrations increase on Day 1. How is this explained? Were replicate measurements performed?
- The manuscript refers to differences in logK values; however, these do not appear to be significant in the figures. Please provide a statistical analysis to determine whether the variations are significant.
- In Figure 5b, how do the authors explain that sFe concentrations exceed cFe concentrations?
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I hope this constructive revision will help the authors to improve the manuscript.
Regards
Citation: https://doi.org/10.5194/egusphere-2025-1798-RC1
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