Platinum enrichment and phase associations in marine ferromanganese crusts and nodules based on a multi-method approach

Koschinsky, Andrea; Hein, James R.; Kraemer, Dennis; Foster, Andrea L.; Kühn, Thomas; Halbach, Peter

doi:10.1016/j.chemgeo.2019.119426

Cited by 34 publications

(35 citation statements)

References 58 publications

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“…In addition, X-ray absorption near-edge structure and extended X-ray absorption fine structure measurements further indicate that redox-sensitive elements, such as Co, Ce and Te, which are found bound in hydrogenetic nodules and crusts, are present in a higher oxidation state than in the overlying ocean water. This observation confirms that the exceptionally high concentration of such metals in polymetallic nodules results from redox processes involving Mn oxide 31,35,60,64,65,68 . By contrast, other elements (such as Pb) remain divalent during surface adsorption and incorporation 68 .…”

Section: Formation Controls On Nodule Chemistry the Mn Oxidessupporting

confidence: 76%

“…Recent synchrotron-based methods, such as X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy, built on prior statistical analysis, experimental work and thermodynamic models to demonstrate that metal enrichment and the structural incorporation of minor and trace metals in deep-ocean polymetallic nodules is controlled by the mineralogy of the nodule [60][61][62][63][64][65] . As a result, noduleformation processes -hydrogenetic versus diagenetic precipitation -that control the mineralogy of the polymetallic nodules also govern their chemical composition 1,2,39,41 .…”

Section: Formation Controls On Nodule Chemistry the Mn Oxidesmentioning

confidence: 99%

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Deep-ocean polymetallic nodules as a resource for critical materials

Hein

Koschinsky

Kühn

2020

Nat Rev Earth Environ

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226

127

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Deep-ocean polymetallic nodules (also known as manganese nodules) are composed of iron and manganese oxides that accrete around a nucleus on the vast abyssal plains of the global ocean 1-6. Polymetallic nodules vary in diameter from less than one to tens of centi metres and acquire economically interesting quantities of critical metals (metals that are essential to the security and economic wellbeing of a nation) from ocean water and/or sediment pore waters. As a result, the enormous quantities of these nodules-which are conservatively estimated to total 21 billion dry tons in the Clarion-Clipperton Zone 7,8 (CCZ; located in the northeast equatorial Pacific Ocean) alone (Fig. 1)-host considerable tonnages of critical metals that are essential for green energy, vehicles and infrastructure, as well as for new technology and military applications. This reservoir of critical metals has, therefore, triggered interest in new deep-ocean mining operations. However, the potential environmental impacts of such activities are of great concern and have hastened extensive research and evaluation in this area 9-11. Polymetallic nodules were first discovered on the seabed at a depth of approximately 4,300-5,500 m during the 1872-1876 voyage of the HMS Challenger to study the deep ocean 12. A number of nodules, which contained numerous shark teeth and cetacean ear bones, were collected from the western end of the CCZ nodule field 12. Early hypotheses suggested that polymetallic nodules form by alteration of volcanic rocks and grains, especially glass, which are transformed into manganese carbonates and, finally, into oxides that are deposited from solution to form nodules on water-rich sediments 12-14. However, later work-aided in part by the 1957-1958 International Geophysical Year-revealed the general source of the metals (seawater and sediment pore water) and the sorption processes that might be involved in the acquisition of minor metals by nodules 15-20. Economic interest in the deep-ocean polymetallic nodules developed in the 1960s 15,16 , which subsequently led to the formation of consortia in Germany,

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Section: Formation Controls On Nodule Chemistry the Mn Oxidessupporting

confidence: 76%

Section: Formation Controls On Nodule Chemistry the Mn Oxidesmentioning

confidence: 99%

Deep-ocean polymetallic nodules as a resource for critical materials

Hein

Koschinsky

Kühn

2020

Nat Rev Earth Environ

Self Cite

226

127

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“…While both of these explanations could plausibly explain the high‐relative abundance of asbolane that we determined using EXAFS, it is more likely that the significant similarity in the Mn bonding environment (hexagonal MnO 6 sheets) that gives asbolane a very similar EXAFS spectrum to vernadite, and thus is likely overrepresented in our EXAFS fits (Tables 3 and 6) (Post, 1999). Additionally, the relative abundance of Ni and Co in CD29 (∼1–2 wt%) is likely insufficient to support such a significant asbolane fraction (Frank et al., 1999; Koschinsky et al., 2020; Manceau et al., 1992b). Therefore, the most parsimonious interpretation of the Mn mineralogy of CD29 includes a primary deposition of a highly disordered phyllomanganate (consisting of mixed hexagonal and triclinic symmetry, mostly as vernadite) and a Mn(III) oxyhydroxide such as feitknechite.…”

Section: Discussionmentioning

confidence: 99%

Spectroscopic Insights Into Ferromanganese Crust Formation and Diagenesis

Sutherland

Wankel

Hein

et al. 2020

Geochem Geophys Geosyst

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Marine ferromanganese deposits, including both crusts and nodules, form in all five global ocean basins at almost every latitude (Cronan, 1977; Hein et al., 1997, 2000). Ferromanganese deposits have classically been categorized into one of three groups based on mode of formation and trace element associations: hydrogenetic deposits, diagenetic deposits, and hydrothermal deposits. Hydrogenetic ferromanganese deposits precipitate in direct contact with the water column on the surface of a substrate rock or existing crust or nodule

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“…According to a recent study, the Pt content in marine ferromanganese crusts ranges from 44 to 3207 ppb and the averaged value is 314 ppb (N = 182). 57 The dissolved Pt concentration in the Pacific Ocean shows a nutrient-type profile, and the Pt concentration increases with depth, from 100 pg/L in shallow waters to approximately 300 pg/L in deeper water. Pt in seawater exists as negatively-charged complexes with OHand Clas the dominant ligands: [Pt(OH)nCl4-n] 2-.…”

Section: •2•1 Platinum (Pt 4 F Xps Pt L3-edge Xas)mentioning

confidence: 99%

Investigations on Adsorption of Inorganic Ions in Aqueous Solution to Some Metal Oxides, Hydroxides and a Carbonate by the X-Ray Spectroscopic Method

et al. 2021

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Why does the adsorption and concentration of inorganic chemical species proceed at aqueous-solid interfaces? In this review paper, we discuss the use of X-ray chemical state analysis to elucidate the intrinsic adsorption mechanism. Based on the chemical states of the species adsorbed to solids as determined by X-ray chemical state analysis, possible adsorption mechanisms are discussed. The driving forces of adsorption are represented by the Gibbs free energy change (ΔGchem = ΔGchem,1 + ΔGchem,2) resulting from the formation of covalent bonds between metal ions (M) in metal oxides or hydroxides and adsorbed species (X) (M-O-X bond, ΔGchem,1) and the formation of new phases consisting of M and X (ΔGchem,2). The concept of ΔGchem,2 is proposed based on the experimental results from chemical state analyses. As examples, the following investigations are discussed in this review paper: the formation of mullite precursors by the adsorption of monosilicic acid to Al(OH)3, the spontaneous reduction of Au(III) to Au(0) by adsorption of Au(III) to Al(OH)3, MnO2 and Ni(OH)2 and the mechanism of concentration of Co 2+ , Tl + , Pb 2+ , Pt 2+ , Au + , and Pd 2+ in marine ferromanganese crusts.

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Platinum enrichment and phase associations in marine ferromanganese crusts and nodules based on a multi-method approach

Cited by 34 publications

References 58 publications

Deep-ocean polymetallic nodules as a resource for critical materials

Deep-ocean polymetallic nodules as a resource for critical materials

Spectroscopic Insights Into Ferromanganese Crust Formation and Diagenesis

Investigations on Adsorption of Inorganic Ions in Aqueous Solution to Some Metal Oxides, Hydroxides and a Carbonate by the X-Ray Spectroscopic Method

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