Nickel exchange between aqueous Ni(II) and deep-sea ferromanganese nodules and crusts

Hens, Tobias; Brugger, Joël; Paterson, David L.; Brand, Helen E. A.; Whitworth, Anne J.; Frierdich, Andrew J.

doi:10.1016/j.chemgeo.2019.119276

Cited by 8 publications

(7 citation statements)

References 96 publications

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“…It is possible, therefore, that structural incorporation of Ni is associated with a different isotope effect than adsorption as a surface complex. A second explanation relates to reaction kinetics, with slow-growing (a few mm/Ma) Fe-Mn crusts exhibiting long-term isotopic equilibration of Ni with seawater; exchangeability of Ni in Fe-Mn crusts has recently been demonstrated by Hens et al (2019). Finally, it has been suggested that Ni speciation in seawater may control the isotopic composition of the sorbing Ni species, with a possible role for organic complexation (Sorensen et al, 2020).…”

Section: Manganese Cyclingmentioning

confidence: 99%

Towards balancing the oceanic Ni budget

Little

Archer

McManus

et al. 2020

Earth and Planetary Science Letters

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Nickel isotopes are a novel and promising tracer of the chemistry of past ocean environments, but realisation of this tracer's potential requires a comprehensive understanding of the controls on Ni burial in the marine sedimentary archive. An outstanding puzzle in the marine budget of Ni, first recognised in the 1970s, is a major imbalance in the known inputs and outputs to and from the ocean: the sedimentary outputs of Ni are much larger than the inputs (rivers, dust). Much more recently, it has also been recognised that the outputs are also considerably isotopically heavier than the inputs. In this study, we find light Ni isotope compositions (δ 60 Ni NIST SRM986 = -0.2 to -0.8‰) for Mn-rich sediments from the eastern Pacific compared to Fe-Mn crusts (at about +1.6‰). These data suggest that diagenetic remobilisation of isotopically heavy Ni leads to a significant benthic Ni flux (estimated at 0.6 -2.3 x 10 8 mol/yr), similar in magnitude to the riverine flux, to the ocean. Diagenetic remobilisation of Ni may occur either via cycles of Mn-oxide dissolution and precipitation, with associated Ni sorption and release, or during mineralogical transformation of birnessite to todorokite. A minor role for retention of isotopically light Ni by Fe oxides or Fe-rich authigenic clays is also proposed. Overall, a benthic flux of isotopically heavy Ni (at about +3‰) can balance the marine Ni budget, pinpointing diagenesis as a key missing piece of the Ni puzzle.

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Section: Manganese Cyclingmentioning

confidence: 99%

Towards balancing the oceanic Ni budget

Little

Archer

McManus

et al. 2020

Earth and Planetary Science Letters

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“…Deviations from the expected intensity ratio at high intensities do not reflect changes in Ce oxidation state, but rather are due to self-absorption, i.e. result from high Ce concentrations in regions R3 and R4 (Hens et al , 2019). In the spectra, this is reflected by a lowering of the intensity of the white line (intense peak in the spectrum of Ce(III) compounds) due to peak broadening (Fig.…”

Section: Methodology and Resultsmentioning

confidence: 99%

An in situ, micro-scale investigation of inorganically and organically driven rare-earth remobilisation during weathering

Kalintsev

Brugger

Ram

2021

MinMag

Self Cite

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At present, a significant portion of rare-earth elements (REEs) are sourced from weathering profiles. The mineralogy of the protolith plays an important role in controlling the fate of REEs during weathering, as accessory minerals contain the bulk the REE budget in most rocks, and different minerals vary in their susceptibilities to weathering processes. REE supergene deposits (‘adsorption clay deposits’) are associated with deep weathering in tropical environments, which often precludes characterisation of the incipient steps in REE liberation from their host minerals in the protolith. Here we have targeted a weathered REE-enriched lithology from a sub-arid environment undergoing relatively rapid uplift, namely the Yerila Gneiss from the Northern Flinders Ranges, Australia, where regolith was shallow or absent and parent rock material had yet to completely break down. Results from X-ray fluorescence mapping, scanning electron microscopy (SEM), SEM-focussed ion beam milling (FIB-SEM), inductively-coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS highlight the migration pathways of REEs and associated U and Th from allanite-(Ce) grains that are the main REE host within Yerila Gneiss material. Migration of light REEs and Th away from the allanite-(Ce) grains via radial cracks resulting from allanite-(Ce) metamictisation was interpreted to result from weathering, as Ce is partially present in its tetravalent oxidation state and Th mobility is most easily explained by the involvement of organic ligands. FIB-SEM provides further evidence for the importance of biogenic processes in REE+U/Th mobility and fractionation in uranothorite-associated spheroidal structures associated with the weathering of allanite-(Ce). Organic carbon was also found in association with a xenotime-(Y) grain; in this case, REE liberation is most likely a by-product of biogenic phosphate utilisation. These results highlight that local controls (at mineral interfaces) mediated by biota and/or biogenic organic matter can control the initiation of REE (+Th,U) mobilisation during weathering.

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“…Oceanic Fe-Mn crusts and nodules mainly consist of layered vernadite, buserite and 3-D tunneled todorokite, which are made up of octahedral MnO 6 nano-units and amorphous FeOOH that are intergrown with the Mn oxides [10,16,[107][108][109]. The MnO 6 octahedrons comprise the Mn layer and the Mn tunnel structures, and they facilitate many isomorphic substitutions through Mn 4+ or Mn 3+ replacements and exhibit many vacant sites in the structures, i.e., unfilled empty octahedrons in the layer that attracts metal fillings [13,14,105,110,111]. The electro-charge deficits from low-valent cation replacements (e.g., Co 2+ → Mn 4+ ) can be balanced and compensated by the incorporations of hydrated cations in the interlayer or the tunnel center (e.g., Mg 2+ , Ca 2+ , Zn 2+ , Li + , Na + ).…”

Section: Structural Uptakementioning

confidence: 99%

Enrichment Characteristics and Mechanisms of Critical Metals in Marine Fe-Mn Crusts and Nodules: A Review

Huang,

2023

Minerals

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Marine Co-rich ferromanganese crusts and polymetallic nodules, which are widely distributed in oceanic environments, are salient potential mineral resources that are enriched with many critical metals. Many investigations have achieved essential progress and findings regarding critical metal enrichment in Fe-Mn crusts and nodules. This study systematically reviews the research findings of previous investigations and elaborates in detail on the enrichment characteristics, enrichment processes and mechanisms and the influencing factors of the critical metals enriched in Fe-Mn crusts and nodules. The influencing factors of critical metal enrichments in Fe-Mn crusts and nodules mainly include the growth rate, water depth, post-depositional phosphatization and structural uptake of adsorbents. The major enrichment pathways of critical metals in marine Fe-Mn (oxy)hydroxides are primarily as follows: direct substitution on the surface of δ-MnO2 for Ni, Cu, Zn and Li; oxidative substitution on the δ-MnO2 surface for Co, Ce and Tl; partition between Mn and Fe phases through surface complexation according to electro-species attractiveness for REY (except for Ce), Cd, Mo, W and V; combined Mn-Fe phases enrichment for seawater anionic Te, Pt, As and Sb, whose low-valence species are mostly oxidatively enriched on δ-MnO2, in addition to electro-chemical adsorption onto FeOOH, while high-valence species are likely structurally incorporated by amorphous FeOOH; and dominant sorption and incorporation by amorphous FeOOH for Ti and Se. The coordination preferences of critical metals in the layered and tunneled Mn oxides are primarily as follows: metal incorporations in the layer/tunnel-wall for Co, Ni and Cu; triple-corner-sharing configurations above the structural vacancy for Co, Ni, Cu, Zn and Tl; double-corner-sharing configurations for As, Sb, Mo, W, V and Te; edge-sharing configurations at the layer rims for corner-sharing metals when they are less competitive in taking up the corner-sharing position or under less oxidizing conditions when the metals are less feasible for reactions with layer vacancy; and hydrated interlayer or tunnel-center sorption for Ni, Cu, Zn, Cd, Tl and Li. The major ore-forming elements (e.g., Co, Ni, Cu and Zn), rare earth elements and yttrium, platinum-group elements, dispersed elements (e.g., Te, Tl, Se and Cd) and other enriched critical metals (e.g., Li, Ti and Mo) in polymetallic nodules and Co-rich Fe-Mn crusts of different geneses have unique and varied enrichment characteristics, metal occurrence states, enrichment processes and enrichment mechanisms. This review helps to deepen the understanding of the geochemical behaviors of critical metals in oceanic environments, and it also bears significance for understanding the extreme enrichment and mineralization of deep-sea critical metals.

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Nickel exchange between aqueous Ni(II) and deep-sea ferromanganese nodules and crusts

Cited by 8 publications

References 96 publications

Towards balancing the oceanic Ni budget

Towards balancing the oceanic Ni budget

An in situ, micro-scale investigation of inorganically and organically driven rare-earth remobilisation during weathering

Enrichment Characteristics and Mechanisms of Critical Metals in Marine Fe-Mn Crusts and Nodules: A Review

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