Marine Phosphorites as Potential Resources for Heavy Rare Earth Elements and Yttrium

Hein, James R.; Koschinsky, Andrea; Mikesell, Mariah; Mizell, Kira; Glenn, Craig R.; Wood, Ray

doi:10.3390/min6030088

Cited by 61 publications

(48 citation statements)

References 30 publications

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“…Other elements in high concentration in the phosphatized RGR crusts were Li (30.9-217, mean 127 ppm), which was much more enriched compared to the non-phosphatized crust, and the %HREY (29.1-50.2%, mean 40.8%), which was also very high compared to the non-phosphatized crusts and similar to the range determined for marine phosphorites by [49]. The highest individual REY concentrations were Ce (34.1-426, mean 195 ppm), Y (40.7-802, mean 237 ppm), La (23.0-370, mean 120 ppm), and Nd (16.1-324, mean 99.8 ppm).…”

Section: Phosphatized Fe-mn Crustssupporting

confidence: 79%

“…Substitution might also be the reason for HREY enrichments. Yttrium (Y 3+ ) and the REE 3+ replace Ca 2+ in the CFA structure [49,96], which is consistent with the positive correlation between the REY (excepting Ce) and P, especially for Y. [49] found that the %HREY of the total REY complement from seamount phosphorites is higher than in associated Fe-Mn crusts, due to different mechanisms of REE incorporation.…”

Section: Influence Of Phosphatization On the Chemical Composition Of supporting

confidence: 68%

“…Aluminum enrichment is unexpected since it usually shows a strong depletion in phosphatized crusts [55]. The aluminum content of seamount phosphorites increases with increasing biogenic silica [49] since Al is a component of silica frustules of diatoms in variable amounts [92]. In this case, we would expect an enrichment of Si in the phosphatized crust of equal magnitude as Al, which is not found because the Si phases likely underwent replacement preferentially over Al phases during phosphatization [55].…”

Section: Influence Of Phosphatization On the Chemical Composition Of mentioning

confidence: 95%

“…The enrichment in Cd contents in the phosphatized RGR crusts suggests a high input of biological material. Additionally, Cd enrichment in phosphatized crusts from the Ninetyeast Ridge in the Indian Ocean was suggested to reflect the replacement of Cd 2+ for Ca 2+ in the CFA due to their similar ionic radius [49].…”

Section: Influence Of Phosphatization On the Chemical Composition Of mentioning

confidence: 99%

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Genesis and Evolution of Ferromanganese Crusts from the Summit of Rio Grande Rise, Southwest Atlantic Ocean

et al. 2020

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The Rio Grande Rise (RGR) is a large elevation in the Atlantic Ocean and known to host potential mineral resources of ferromanganese crusts (Fe–Mn), but no investigation into their general characteristics have been made in detail. Here, we investigate the chemical and mineralogical composition, growth rates and ages of initiation, and phosphatization of relatively shallow-water (650–825 m) Fe–Mn crusts dredged from the summit of RGR by using computed tomography, X-ray diffraction, 87Sr/86Sr ratios, U–Th isotopes, and various analytical techniques to determine their chemical composition. Fe–Mn crusts from RGR have two distinct generations. The older one has an estimated age of initiation around 48–55 Ma and was extensively affected by post-depositional processes under suboxic conditions resulting in phosphatization during the Miocene (from 20 to 6.8 Ma). As a result, the older generation shows characteristics of diagenetic Fe–Mn deposits, such as low Fe/Mn ratios (mean 0.52), high Mn, Ni, and Li contents and the presence of a 10 Å phyllomanganate, combined with the highest P content among crusts (up to 7.7 wt %). The younger generation is typical of hydrogenetic crusts formed under oxic conditions, with a mean Fe/Mn ratio of 0.75 and mean Co content of 0.66 wt %, and has the highest mean contents of Bi, Nb, Ni, Te, Rh, Ru, and Pt among crusts formed elsewhere. The regeneration of nutrients from local biological productivity in the water column is the main source of metals to crusts, providing mainly metals that regenerate rapidly in the water column and are made available at relatively shallow water depths (Ni, As, V, and Cd), at the expense of metals of slower regeneration (Si and Cu). Additionally, important contributions of nutrients may derive from various water masses, especially the South Atlantic Mode Water and Antarctic Intermediate Water (AAIW). Bulk Fe–Mn crusts from the summit of RGR plateau are generally depleted in metals considered of greatest economic interest in crusts like Co, REE, Mo, Te, and Zr, but are the most enriched in the critical metals Ni and Li compared to other crusts. Further investigations are warranted on Fe–Mn crusts from deeper-water depths along the RGR plateau and surrounding areas, which would less likely be affected by phosphatization.

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Section: Phosphatized Fe-mn Crustssupporting

confidence: 79%

Section: Influence Of Phosphatization On the Chemical Composition Of supporting

confidence: 68%

Section: Influence Of Phosphatization On the Chemical Composition Of mentioning

confidence: 95%

Section: Influence Of Phosphatization On the Chemical Composition Of mentioning

confidence: 99%

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Genesis and Evolution of Ferromanganese Crusts from the Summit of Rio Grande Rise, Southwest Atlantic Ocean

et al. 2020

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“…Normalized to PAAS chemical microprobe analyses of DHR hydroxylapatite, indicate negative Ce anomaly [43]. The REE pattern is typical for seamount phosphorites (Figure 11; compare [108]), as well as land-based phosphorites. Besides hydroxylapatite, some traces of Y (24-44 ppm) were also identified in stratified phyllosilicates (glauconite, Fe-smectite and Fe-chlorite) and K-phillipsite (140-320 ppm).…”

Section: Phosphatesmentioning

confidence: 99%

Mineralogy of Cobalt-Rich Ferromanganese Crusts from the Perth Abyssal Plain (E Indian Ocean)

et al. 2019

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Mineralogy of phosphatized and zeolitized hydrogenous cobalt-rich ferromanganese crusts from Dirck Hartog Ridge (DHR), the Perth Abyssal Plain (PAP), formed on an altered basaltic substrate, is described. Detail studies of crusts were conducted using optical transmitted light microscopy, X-ray Powder Diffraction (XRD) and Energy Dispersive X-ray Fluorescence (EDXRF), Differential Thermal Analysis (DTA) and Electron Probe Microanalysis (EPMA). The major Fe-Mn mineral phases that form DHR crusts are low-crystalline vernadite, asbolane and a feroxyhyte-ferrihydrite mixture. Accessory minerals are Ca-hydroxyapatite, zeolites (Na-phillipsite, chabazite, heulandite-clinoptilolite), glauconite and several clay minerals (Fe-smectite, nontronite, celadonite) are identified in the basalt-crust border zone. The highest Ni, Cu and Co contents are observed in asbolane and Mn-(Fe) vernadite. There is significant enrichment of Ti in feroxyhyte−ferrihydrite and vernadite. The highest rare earth element (REE) content is measured in the phosphate minerals, less in phyllosilicates and Na-phillipsite. The geochemical composition of minerals in the DHR crusts supports the formation of crusts by initial alteration, phosphatization and zeolitization of the substrate basalts followed by oscillatory Fe-Mn oxyhydroxides precipitation of hydrogenous vernadite (oxic conditions) and diagenous asbolane (suboxic conditions).Minerals 2019, 9, 84 2 of 33 hydrothermal fluids), the two major types of ferromanganese crusts are distinguished: (I) hydrogenetic cobalt-rich ferromanganese crusts; (II) hydrothermal crusts and encrustations (sometimes called stratabound manganese oxides) [15][16][17][18]. Hydrothermal crusts that precipitate directly from low temperature hydrothermal fluids (few tens of degrees up to 200 • C), usually grow significantly faster, even up to 1600-1800 mm/Ma [19]. Ferromanganese crusts in some locations form through a combination of fluid sources and thereby exhibit a mixed origin, primarily either hydrogenetic, diagenetic or hydrothermal-hydrogenetic [15,18,20,21].Co-rich ferromanganese crusts formation is dominated by hydrogenetic processes. The precipitation from bottom waters is extremely slow, with growth rates of 1-5 mm/Ma. The thickest crusts occur in the depth interval between 800-2500 m and show the highest concentrations of critical metals [22]. Some authors limit this depth to the anoxic zone at approximate depths of 1000-1500 m. Below these depths, the thickness of crusts decrease [23][24][25].On the youngest rock outcrops, crusts form mainly patina-thin layers. Most crust surfaces are either botryoidal, smooth or rough, that form under conditions of strong bottom currents. In the thick crusts, 2 to 8 visible or macroscopic layers may be distinguished. The internal layers are usually black and massive, while outer parts are slightly lighter, laminated and more porous [13]. However, crusts with four major layers of oxide layers have been found. The outer-and innermost are massive and show light colors, whereas the...

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Invertebrate trophic structure on marine ferromanganese and phosphorite hardgrounds

Pereira,

Vlach,

Bradley

et al. 2024

Limnology & Oceanography

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The Southern California Borderland hosts a variety of geologic and oceanographic features that allow for diverse habitats to occur in a restricted region with a strong oxygen minimum zone (OMZ) and hard substrates. These include ferromanganese (FeMn) crusts and phosphorites targeted for deep‐seabed mining in other regions. Baseline studies regarding hardground macro‐ (> 0.3 mm) and megafaunal (> 2 cm) invertebrates are lacking, although they contribute to understanding nutrient cycling and resilience of deep‐sea communities to ocean deoxygenation, fishing, or mineral extraction. With the goal of understanding how substrate type, depth, and dissolved oxygen concentration influence invertebrate trophic structure, we surveyed δ13C and δ15N values of invertebrates on hard substrates on the Southern California Borderland margin along a depth gradient (120–2400 m) through the OMZ at inshore (< 100 km from shore) and offshore (100–250 km from shore) sites, using generalized additive models and community‐level metrics. Macrofaunal isotopic values correlate with substrate type, exhibiting higher trophic diversity on FeMn crusts and specialized communities on phosphorites. Megafaunal isotopic values correlate with proximity to shore; animals offshore seem to depend more on phytoplanktonic production than animals inshore. In general, δ15N increased with decreasing dissolved oxygen and increasing depth, possibly due to remineralization processes within the OMZ and with depth. We discuss how feeding modes and community composition might influence the observed patterns. This study elucidates the importance of the environmental context in shaping invertebrate trophic structure on continental margins and provides baseline knowledge that may be useful in regions where these minerals are targeted for extraction.

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Marine Phosphorites as Potential Resources for Heavy Rare Earth Elements and Yttrium

Cited by 61 publications

References 30 publications

Genesis and Evolution of Ferromanganese Crusts from the Summit of Rio Grande Rise, Southwest Atlantic Ocean

Genesis and Evolution of Ferromanganese Crusts from the Summit of Rio Grande Rise, Southwest Atlantic Ocean

Mineralogy of Cobalt-Rich Ferromanganese Crusts from the Perth Abyssal Plain (E Indian Ocean)

Invertebrate trophic structure on marine ferromanganese and phosphorite hardgrounds

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