Fe-Mn Crusts Research Articles

Uncovering the oxic-suboxic microenvironment change in seamount flank through authigenic clay minerals in basaltic substrate of ferromanganese crust, Magellan seamount

In low-temperature ocean environments, basalt alteration by seawater precipitates authigenic clay minerals that serve as proxies for reconstructing paleo-ocean conditions because they reflect surrounding oxic-suboxic conditions. In this study, alteration rims on basaltic substrate associated with ferromanganese (Fe-Mn) crust from the Magellan seamount KC-7 were identified by microscopic analyses. Mineralogical and geochemical analyses indicate that the alteration rims contain K-enriched Fe-smectite and glauconite which suggest that seawater-basalt interaction occurred under oxic conditions and in the presence of organic-rich suboxic conditions, respectively. These disparate environmental conditions suggest that the environment changed before and after Fe-Mn crusts formed. During the Cenozoic hyperthermal events, oxygen-rich bottom water was supplied by upwelling driven by the geomorphological influence of the seamounts, which may have led to basalt alteration. The K-enriched Fe-smectites, which indicate oxic condition, formed via seawater-basalt interactions before the Fe-Mn crust incrustation. Later, during the Eocene, the opening of the Drake Passage enhanced the supply of oxygen-rich seawater to the Magellan Seamounts, thereby enabling the formation of hydrogenetic Fe-Mn crust. After the incrustation of seamount flanks with Fe-Mn crusts, the carbonate fluorapatite (CFA), a product of the global phosphatization event, filled the pores in the Fe-Mn crusts during Oi-1 glaciation. As a result, seawater-basalt interactions decreased and led to suboxic conditions, in which glauconite formed as organic matter was remineralized under the organic-rich conditions in the basaltic substrate. This authigenic clay mineral formation sequence suggests that changes in ocean circulation and subsequent changes in the oxic-suboxic conditions in the basaltic substrate occurred on the western Pacific seamount KC-7.

Miocene Petit-Spot Basanitic Volcanoes on Cretaceous Alba Guyot (Magellan Seamount Trail, Pacific Ocean)

New data obtained from core samples of two boreholes and dredged samples from the Alba Guyot in the Magellan Seamount Trail (MST), Western Pacific, including the 40Ar/39Ar age determinations of basanite, and the mineralogy of basanite, tuff, tuffite, mantle-derived inclusions in basanite and tuff (lherzolite xenolith and Ol, Cpx, and Opx xenocrysts), and calcareous nannofossil biostratigraphy, have implications for the guyot′s development and history. Volcanic units in the upper part of the Alba Guyot main edifice and its Oma Vlinder satellite, at sea depths between 3600 and 2200 m, were deposited during the Cretaceous 112 to 86 Ma interval. In the following ~60 myr, the Alba Guyot became partly submerged and denuded with the formation of a flat summit platform while the respective fragment of the Pacific Plate was moving to the Northern Hemisphere. Volcanic activity in the northeastern part of the guyot summit platform was rejuvenated in the Miocene (24–15 Ma) and produced onshore basanitic volcanoes and layers of tuff in subaerial and tuffite in shallow-water near-shore conditions. In the Middle-Late Miocene (10–6 Ma), after the guyot had submerged, carbonates containing calcareous nannofossils were deposited on the porous surfaces of tuff and tuffite. Precipitation of the Fe-Mn crust (Unit III) recommenced during the Pliocene–Pleistocene (<1.8 Ma) when the guyot summit reached favorable sea depths. The location of the MST guyots in the northwestern segment of the Pacific Plate near the Mariana Trench, along with the Miocene age and alkali-basaltic signatures of basanite, provide first evidence for petit-spot volcanism on the Alba Guyot. This inference agrees with the geochemistry of Cenozoic petit-spot basaltic rocks from the Pacific and Miocene basanite on the Alba Guyot. Petit-spot volcanics presumably originated from alkali-basaltic melts produced by decompression partial melting of carbonatized peridotite in the metasomatized oceanic lithosphere at the Lithosphere–Asthenosphere Boundary level. The numerous volcanic cones with elevations of up to 750 m high and 5.1 km in basal diameter, discovered on the Alba summit platform, provide the first evidence of voluminous Miocene petit-spot basanitic volcanism upon the Cretaceous guyots and seamounts of the Pacific.

Biogenic Origin of Fe-Mn Crusts from Hydrothermal Fields of the Mid-Atlantic Ridge, Puy de Folles Volcano Region

Ferromanganese formations are widespread in the Earth’s aquatic environment. Of all the mechanisms of their formation, the biogenic one is the most debatable. Here, we studied the Fe-Mn crusts of hydrothermal fields near the underwater volcano Puy de Folles (rift valley of the Mid-Atlantic Ridge). The chemical and mineralogical composition (optical and electron microscopy with EDX, X-ray powder diffraction, X-ray fluorescence analysis, Raman and FTIR spectroscopy, gas chromatography—mass spectrometry (GC-MS)) and the magnetic properties (static and resonance methods, including at cryogenic temperatures) of the samples of Fe-Mn crusts were investigated. In the IR absorption spectra, based on hydrogen bond stretching vibrations, it was concluded that there were compounds with aliphatic (alkane) groups as well as compounds with double bonds (possibly with a benzene ring). The GC-MS analysis showed the presence of alkanes, alkenes, hopanes, and steranes. Magnetically, the material is highly coercive; the blocking temperatures are 3 and 13 K. The main carriers of magnetism are ultrafine particles and X-ray amorphous matter. The analysis of experimental data allows us to conclude that the studied ferromanganese crusts, namely in their ferruginous phase, were formed as a result of induced biomineralization with the participation of iron-oxidizing and iron-reducing bacteria.

Episodic intensification of marine phosphorus burial over the last 80 million years

Marine phosphatization events cause episodic carbonate fluorapatite (CFA) precipitation on seamounts, and are commonly linked to growth hiatuses in ferromanganese (Fe-Mn) crusts. However, the complete record of these events and their paleoenvironmental significance remains poorly understood, in large part due to poor age constraints. Here, we apply U-Pb dating to CFA in Fe-Mn crusts from Western Pacific seamounts. These data exhibit good alignment with Sr isotope ages, revealing six potential phosphatization events. This established CFA chronology tightens the timespan of phosphatization events and refines the age framework of Fe-Mn crusts. We subsequently utilize a multiproxy approach to demonstrate that the phosphatization events occurred coeval with the expansion of oceanic oxygen minimum zones. The Western Pacific Fe-Mn crusts thus document major perturbations in global oceanic phosphorus cycling, which appear to have been driven by climate-induced increases in primary productivity linked to changes in global ocean circulation.

Balancing the oceanic Zn isotope budget: The key role of deep-sea pelagic sediments

Abstract Oxygenated deep-sea pelagic sediments with Fe-Mn–oxide particles represent a key oceanic oxic sink for transition metals in the modern ocean. However, the isotopic composition of authigenic Zn in the pelagic zone remains poorly constrained, which hampers our understanding of the global budget of Zn isotopes. Here, we analyzed the Zn isotopic compositions of two deep-sea pelagic sediment columns collected from the Pacific Ocean. The results show that authigenic Zn in deep-sea sediments is primarily hosted by the Fe-Mn (oxyhydr)oxides. The light Zn isotopic signatures (δ66Zn: −0.02‰ to 0.34‰, n = 42; computed as the per mille deviation of the 66Zn/64Zn ratio from the JMC-Lyon standard) observed in deep-sea sediments are completely different from the previously assumed values of ~1.0‰ based on the Zn isotopic compositions of Fe-Mn crusts and nodules. Based on this observation (Zn flux of deep-sea sediments = 5.3 × 108 mol yr–1), we propose a new, balanced global budget for Zn isotopes.

Invertebrate trophic structure on marine ferromanganese and phosphorite hardgrounds

AbstractThe 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.

Magnetization of Ferromanganese Crusts: Geochemical and Magnetic Insights From Rio Grande Rise and Tropic Seamount

AbstractFerromanganese (FeMn) crusts are Fe and Mn oxides that typically form on deep‐sea elevations by deposition of colloids from seawater. These mineral deposits are considered a source of critical metals and rare earth elements. Besides their potential economic value, FeMn crusts are extremely relevant in ocean science, since their very slow growth rates result in long‐term paleoenvironmental and paleoceanographic records. In this study, we applied geochemical, mineralogical, and magnetic analyses to unravel paleoenvironmental changes at two locations on opposite sides of the Atlantic Ocean, the Rio Grande Rise in the SW Atlantic and the Tropic Seamount in the NE Atlantic. Our results show that the occurrence of amorphous (non‐crystalline) Fe oxyhydroxides and the absence of Fe oxides in hydrogenetic, non‐phosphatized FeMn crusts prevented the development of primary remanent magnetization. In contrast, phosphatized FeMn crusts may have contained a remanent magnetic signal. Phosphatization resulted from increased primary productivity and occurred at different stages during the growth of the FeMn crusts, leading to suboxic conditions and partial dissolution of pre‐existing, remanence‐carrying magnetic minerals. Carbonate Fluorapatite (CFA) accumulation in the phosphatized layers of FeMn crusts replaced Fe and Mn, decreasing their magnetic content. Thus, magnetic variations do not reflect a primary magnetization but rather result from geochemical alterations. The loss of primary magnetization may hamper the use of FeMn deposits for magnetostratigraphic purposes.

Platinum-bearing Fe-Mn oceanic crust on basalts: mineralogy and model of formation

Fe-Mn oceanic crust on basalts of the guyot in the Mid-Pacific Seamount (Pacific Ocean, depth 2486 m, chemical composition (wt %): Mn 24.2, Fe 12.6, Ni 0.59, Co 0.72, Cu 0.13; (ppm) Pt 0.35, Pd 0.0052), was studied using 3D-technology of mineralogical research. In addition to dominaiting vernadite and goethite, the following minerals are identified in the hydroseparation (HS) concentrates of the crust: 1) rock forming and accessory minerals of basalts (clinopyroxene, plagioclase, potassium feldspar, biotite, ilmenite, titanomagnetite, Ti-chrome spinel, zircon, apatite); 2) sulfides that are identical to those from the basalt substrate (pyrite, chalcopyrite, bornite, chalcocite, tennantite, nickel pentlandite Ni4S3, sphalerite, galena, argentite/acantite, molybdenite); 3) native metals (iron, nickel, copper, titanium, tungsten); 4) iron silicides (gupeiite Fe3Si, xifengite Fe5Si3, and hapkeite Fe5Si3); 5) platinum group minerals - unnamed (Cu,Pt)4Si and rustenburgite (Pt,Pd)3(Sn,Sb). The complexes of ore minerals in basalts are identical to those of the Fe-Mn crusts. Basalt accessories are assumed to be primary phases and a source of metals for the formation of native minerals. “Microdroplets” of native iron Fe, (Fe,Ni), nickel Ni, (Ni,Cr), (Ni,Fe) and copper Cu (sizes 20–100 microns, degree of sphericity up to 100%) represent the products of their crystallization from metal melts in basalts, transported by deep fluid into Fe-Mn crusts on these rocks. The zoned microglobules of 20–70 microns sizes with iron or native nickel (core) + successive rims of wüstite-magnetite and Fe-Mn hydroxides were identified. They were apparently formed during the movement of these solid microparticles (from bottom to the top) along intergranular spaces and other permeability channels in basalts under conditions of increasing oxygen fugacity and falling temperature at various levels of deep fluid infiltration. The crystallization of native metals in the Fe-Mn crust that are characterized by low-temperature (10 °C) and oxidizing (fO2 MHG magnetite-hematite-goethite) conditions of mineral formation is impossible. The goethite replacement to different extent of many grains of relict Fe-minerals (sulfides and native metals) that are “foreign” to the Fe-Mn crust have been established. Fe-Mn crusts were formed as a result of the precipitation of colloidal particles Mn2+(Ba2+и Sr2+), to a lesser extent of the iron hydroxide Fe(ОН)3, as well as the concentration and transformation of micrograins of minerals of other metals, extracted by fluid from basaltic substrates. The comparison of the physico-chemical parameters of crystallization of basalts and native metals suggests another source of formation of native minerals in basalts, different from the postmagmatic basaltic fluid, i.e. deep-seated sharply reducing "hot" gas flows associated with superplumes. The mineralogical data determines a volcanogenic-fluid-oceanic model for the formation of Fe-Mn crusts on underwater oceanic elevations.

The Rio Grande Rise circulation: Dynamics of an internal tide conversion hotspot in the Southwestern Atlantic

The Rio Grande Rise (RGR) is a plateau located at 31°S in the Southwestern Atlantic, rising from 5916m up to 161m below the sea level. The RGR is an important site for future mining of Fe-Mn crusts and can lead to an expansion of Brazil’s Exclusive Economic Zone. The Cruzeiro do Sul Rift (CSR) fault cuts through the RGR from southeast to northwest. In this study we characterize the RGR circulation, showing that M2 tides are the main source of variability in the region, with an amplitude that can reach 0.3ms−1, larger than the mean flow. These M2 tides are dominated by the baroclinic component and intensified near the bottom. The generation of M2 internal tides occurs mainly in the CSR slopes, with most energy converted from the barotropic tide being radiated away in the form of tidal beams. In addition, the impingement of the mean southern South Equatorial Current and tidal rectification generates anticyclonic circulations around the RGR peaks, with the latter mechanism being responsible for a bottom intensified anticyclonic circulation of 0.2ms−1. Finally, our results reveal that the RGR is a hotspot of internal tide generation in the Southwestern Atlantic.

Petrography and stratigraphic Os isotopic ages of ferromanganese nodules from the Northwest Pacific east of Minamitorishima Island

The area offshore of Minamitorishima Island, Northwestern Pacific Ocean, contains large amounts of seafloor mineral resources such as ferromanganese (Fe–Mn) nodules, Fe–Mn crusts, and rare-earth element and yttrium (REY)-rich muds. In this study, we applied stratigraphic Os isotopic dating to a Fe–Mn nodule for the first time to date its formation/depositional age, and mineralogical and texturally characterized a complementary nodule. Based on macroscopic and microscopic observations, the studied Fe–Mn nodules can be divided into three layers: Layers L2, L1, and L0 from core to rim. Under the microscope, the Fe–Mn nodules are dominated by vernadite and Fe-oxyhydroxide. In particular, Layer L1 is dominated by banded-columnar vernadite and contains lower amounts of clay minerals derived from the detrital component than Layers L2 and L0. The bulk major and trace element geochemical compositions of sampled layers in the Fe–Mn nodules all plotted in the hydrogenous field in several discrimination diagrams. The Os isotopic ages determined by fitting to the paleo-seawater 187Os/188Os curve can be divided into three clusters (35.7–31.0, 19.0–9.0, and 4.0–1.0 Ma, corresponding to Layers L2, L1, and L0, respectively). These Os isotopic ages indicate that two periods of very slow growth or growth hiatuses occurred during the formation of the Fe–Mn nodule; these age gaps are related to the intermittent (discontinuous) timings of the beginning of Fe–Mn nodule formation offshore Minamitorishima Island.

Weathering as a control on the triple oxygen isotopes of groundwater-associated ferromanganese deposits: lessons from the Grimlock Ni–Co–Mn prospect, Northern Territory, Australia

At the Grimlock laterite deposit (Northern Territory, Australia), Co and Ni mineralization occurs mainly in the Mn-oxide rich layers of the ferromanganese (Fe-Mn) crust overlying ultramafic bedrock. Groundwater-associated Fe-Mn crusts consist of mineral (e.g. Mn-oxide, Fe-oxyhydroxide and silicate) groups suitable for studying triple oxygen isotopes and present unique interpretative challenges (e.g. small Mn-oxide fractions relative to Fe-Mn precipitates from other formation environments and extensive weathering). We evaluate triple oxygen isotopes within the context of changes to properties (i.e. mineralogy, major and trace element geochemistry, and degree of weathering) of a lateritic profile. We use pre-existing mineral-water fractionation factors, meteoric water δ 18 O and temperature data to calculate δ 18 O values of fully altered mineralogical endmembers, then, using mass balance, discuss scenarios to elucidate measured whole-rock δ 18 O values. The δ ′ 18 O (′ denotes linearized notation) and Δ ′ 17 O of near-surface samples (0–8 m) are generally lower (mean of 8.892‰) and higher (mean of −0.141‰), respectively, than the δ ′ 18 O (mean of 12.767‰) and Δ ′ 17 O (mean of −0.176‰) of samples from greater depths (19–22 m). At 16–17 m depth, δ ′ 18 O and Δ ′ 17 O are relatively high (means of 17.509 and −0.118‰, respectively). The measured whole-rock δ 18 O values are explainable by substituting lower δ ′ 18 O values for the Mn-oxide and Fe-oxyhydroxide fractions, and higher δ ′ 18 O values for the aluminosilicate fraction, changes coinciding with greater alteration. These results suggest that mineral weathering is primarily responsible for observed variations in the triple oxygen isotopes of groundwater-associated Fe-Mn crusts, rather than variation in the initial source of oxygen incorporated into Mn-oxide. Supplementary material: Grimlock sample photographs, XRD patterns and supplementary figures and tables are available at https://doi.org/10.6084/m9.figshare.c.7071907

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

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.

A Cenozoic Record of Deep Oceanic Zn Isotopic Composition in Ferromanganese Crusts

The zinc (Zn) isotopic composition (δ66Zn) of the deep ocean (>1000 m) can provide insights into the carbon cycle, the biological pump, and hydrothermal activity. However, we have an incomplete view of the temporal and spatial evolution of deep-ocean Zn isotopes. Here, we present new δ66Zn values of Fe-Mn crusts from the Pacific Ocean, which we used to reconstruct the evolution of deep-ocean δ66Zn for the Cenozoic. Our results suggest that the δ66Zn values remain stable in the deep Pacific Ocean at around ~ 0.5‰ through the Cenozoic. Our results limit the extent of change in organic zinc burial through the Cenozoic. However, given uncertainties in the global mass balance and analytical error, variations of roughly 20% in organic zinc burial are still possible.

Geochemistry of Iron-Manganese Crusts of the Bering Sea

The ferromanganese crusts found in the Bering Sea on the Volcanology Massif, the Alpha Fault Zone, and the Shirshov Submarine Ridge that cover the surface of rocky volcanic structures are most likely the product of post-volcanic activity. The present results indicate that the studied ferromanganese formations were formed under the influence of two factors: on the one hand–as a result of slow precipitation of metals from ordinary seawater, on the other hand–under the possible influence of metal-enriched hydrothermal solutions. In microstructural and mineralogical terms, the composition of Fe–Mn crusts of the Bering Sea turned out to be rather monotonous. The ore part is represented mainly by ferruginous vernadite and rarely hematite in combination with amorphous silica, to a lesser extent montmorillonite, calcite, and aragonite. The manganese mineral todorokite, considered a reliable sign of hydrothermal origin of ore crusts, was not detected in our samples. In the studied samples the reduced cerium anomaly (0.87) was established only in one sample, and in other samples its value varies within 1.08–1.89, which is typical for the upper horizons of the ocean water column. At the same time, the europium anomaly is close to neutral, so in 7 samples its value is 0.96–1.03 (average 1.0) and only in three samples it is slightly increased (1.05–1.07), which can be considered a very weak sign of hydrothermal activity. In addition, the presence of gold microinclusions in the ferromanganese phase can indirectly indicate the possible influence of hydrothermal factor on the crust composition.

The role of depositional environment and chemical composition on the triple oxygen isotope ratios of ferromanganese precipitates and their endmember components

Ferromanganese precipitates - crusts, nodules, and hydrothermal deposits – typically exhibit negative Δ'17O values. These deviations are thought to reflect partial incorporation of dissolved atmospheric O2, a component with strongly negative Δ'17O values, seawater oxygen, and deep sea O2 into Mn-oxide minerals, in combination with the other major mineralogical endmember components (Fe-oxyhydroxide and silicate minerals), and kinetic processes such as oxidation at mineral surfaces and biological respiration. Our understanding of the triple oxygen isotope systematics of these materials are limited, however; in the current body of literature, triple oxygen isotope data has only been generated for marine hydrogenetic (i.e., metals accrete directly from seawater) Fe-Mn crusts and Mn nodules. This study evaluates the underlying chemical and environmental factors contributing to the bulk triple oxygen isotopic composition of Fe-Mn precipitates of different genetic types (i.e., hydrothermal, hydrogenetic, mixed-type) from a variety of formation environments (e.g., volcanic arc, pull-apart basin, hotspot, freshwater lake). To improve our understanding of the triple oxygen isotope systematics of natural Fe-Mn precipitates and better constrain the endmember components, we isolate and measure close approximations of the Mn-oxide, Fe-oxyhydroxide, and silicate fractions. Hydrothermal Fe-Mn deposits show greater variation in δ'18O and Δ'17O values (6.0 to 29.6 ‰ and −0.286 to 0.007 ‰, respectively) than hydrogenetic Fe-Mn crusts (5.1 to 11.9 ‰ and −0.200 to −0.086 ‰, respectively). Lacustrine Mn nodule δ'18O and Δ'17O values (5.1 to 8.8 ‰ and −0.230 to −0.090 ‰, respectively) are similar to marine hydrogenetic Fe-Mn crusts, primarily reflecting tropospheric O2. The triple oxygen isotope ratios of nearly pure Mn-oxide samples cluster into distinct groups based on oxygen source, and mass-balance mixing models suggest a significant proportion of incorporated oxygen was photosynthetic in origin. The layered Fe-Mn precipitates in this study show irregular to rhythmic patterns of δ'18O and Δ'17O values depending on formation environment that mostly do not correlate with Mn, Fe, and Si contents. Shale-normalized rare earth element and yttrium (REYSN) patterns and anomalies (CeSN/CeSN*, EuSN/EuSN*, and YSN/HoSN), which can provide insight on formation conditions (e.g., redox, oxygen fugacity, and REY speciation of fluids), are compared with the triple oxygen isotope data. The REYSN anomalies increase from the bottom to the top of the profile of the layered marine sample, suggesting conditions became more oxic over time. Although the triple oxygen isotope ratios correlate with the Eu anomaly in most Fe-Mn precipitates, hydrothermal input can limit their utility as indicators of oxygen fugacity. The triple oxygen isotope ratios of Fe-Mn precipitates reflect complex processes and mixing of multiple sources. Constraining these oxygen sources will assist future studies in interpreting paleoenvironmental conditions (e.g., the saturation state and triple oxygen isotope ratios of dissolved O2 in bottom water) at the time of Fe-Mn precipitate formation.

Mineralogy, geochemistry and genesis of the polymetallic crusts from the Chagos-Laccadive Ridge, Arabian Sea, India

Recent offshore exploration by the Geological Survey of India (GSI) located ferromanganese crusts (FeMn) along the Chagos-Laccadive Ridge (CLR) offshore western continental margin of India. CLR FeMn crusts grew on phosphorite substrate rock (phosphorite cemented sand/silt with moderate carbonate fluorapatite (CFA) cement and goethite). Phosphorite precipitation is the product of intense upwelling and phosphorus regeneration due to organic matter degradation and fish debris dissolution. CLR FeMn crusts are of hydrogenetic origin precipitated in an oxic environment. As a result of hydrogenetic processes under oxic conditions, Fe-vernadite dominated the mineral phase of FeMn crusts. CLR FeMn crusts formed when the North Indian deep-water layer mixed with oxygen-depleted waters from the Arabian Sea, Persian Gulf, and Red Sea. Three genetic layers are identified in the FeMn crusts; Type-I, Type-II, and Type-III developed in response to fluctuation in dissolved oxygen during periods of intensified suboxic bottom waters and monsoon maxima associated with past climatic events in the Arabian Sea. Type-I layers are columnar showing low Mn/Fe ratio (∼1), reflectivity, Mg (average 1.24%), and Ni (average 0.29%). Dendritic Type-II layers show high Mn/Fe ratios (average 12.29), reflectivity, Mg (average 3.51%) and Ni (average 1.69%). Type-III layers show very low Mn/Fe ratios (average 0.21), reflectivity, Mg (average 1.4%) and Ni (average 0.01%) and contain a substantial amount of terrigenous debris of aeolian origin. Elements of economic interest such as Mn, Co, Ni, Cu, Mo, Li, Te, and REY in CLR FeMn crusts are depleted owing to terrigenous contribution.

Factors controlling rare earth element plus yttrium enrichment in Fe[sbnd]Mn crusts from Canary Islands Seamounts (NE Central Atlantic)

Marine minerals are important because concentrate in their structure high contents of strategic and critical elements as rare earth elements. Forty-two samples from eight seamounts of Canary Islands Seamount Province (CISP) have been analyzed in order to evaluate their rare earth elements plus yttrium contents (REY). Highest contents of REY are related to hydrogenetic minerals and essentially Fe-vernadite (on average 3000 μg/g). Diagenetic minerals, on the other hand, show the lowest REY contents with an average content of 260 μg/g. These differences also depend on the growth rates, hydrogenetic minerals with growth rates between 0.5 and 5 mm/Ma allow the incorporation of more REY in their structure. REY contents in studied samples varies depending several factors associated with depth and location, shallowest samples presumably growth near or within the oxygen minimum zone are the most enriched with up to 3800 μg/g due to local enrichment of these elements and the slowest growth rate promoted by the reduced ambient conditions while deeper samples around 3000 m water depth show 2800 μg/g. Location also has a role in REY contents essentially due to the presence of different currents. Samples faced to north are exposed to the more oxygenated waters of the North Atlantic Deep Water and are depleted in REY if compared with deeper samples facing to south to the more oxic Antarctic Bottom Water. Finally, the case of study made on three different seamounts of the CISP show that FeMn crusts from this area could provide on average 130 tons of hydrometallurgical recovered REY (based on 1 km2 areal crust coverage) together with interesting quantity of several other strategic and base elements as Mn, Co, Ni, Cu, V, Mo between others.

Application of random-forest machine learning algorithm for mineral predictive mapping of Fe-Mn crusts in the World Ocean

Mineral prospectivity mapping constitutes an efficient tool for delineating areas of highest interest to guide future exploration. Multiple knowledge-driven approaches have been applied for the creation of prospectivity maps for deep-sea ferromanganese (Fe-Mn) crusts over the last decades. The results of a data-driven approach making use of an extensive data collection exercise on occurrences of Fe-Mn crusts in the World Ocean and recent increase in global marine datasets are presented. A Random Forest machine learning algorithm is applied, and results compared with previously established expert-driven maps. Optimal predictive conditions for the algorithm are observed for (i) a forest size superior to a hundred trees, (ii) a training dataset larger than 10%, and (iii) a number of predictors to be used as nodes superior to two. The confusion matrix and out-of-bag errors on the remaining unused data highlight excellent predictive capabilities of the trained model with a prediction accuracy for Fe-Mn crusts of 87.2% and 98.2% for non-crusts locations, with a Kohen’s K index of 0.84, validating its application for prediction at the World scale. The slope of the seafloor, sediment thickness, sediment type, biological productivity, and abyssal mountain constitute the five strongest explanatory variables in predicting the occurrence of Fe-Mn crusts. Most ‘hand-drawn’ knowledge-driven prospective areas are also considered prospective by the random forest algorithm with notable exceptions along the coast of the American continent. However, poor correlation is observed with knowledge-driven GIS-based criterion mapping as the Random Forest considers un-prospective most target areas from the GIS approach. Overall, the Random Forest prediction performs better in predicting a high chance of Fe-Mn crust occurrence in ISA licensed area than the GIS approach, which constitutes an external validation of the predictive quality of the random forest model.

Microstratigraphic geochemical characteristics of ferromanganese crust from central pacific: Implication for the role of Fe and Mn in REY enrichment

Rare earth elements plus yttrium (REY), well-known critical metals for many new and emerging technologies and as proxies in geological events, are one type of the most important high-tech metals in ferromanganese (Fe-Mn) crusts. The REY(III) are accumulated in Fe-Mn crusts through adsorption by Fe-Mn (oxyhydr)oxides. However, negative correlations between Mn and REY in some Fe-Mn crusts reveal a controversial role of Mn oxides in REY enrichment, which remains equivocal. In this study, texture, structure, mineralogy, and microstratigraphic geochemistry with the growth of a Fe-Mn crust (MP2D32A) from the Line Islands archipelago were analyzed using multiple microanalysis methods. The Fe-Mn crust is characterized by laminar structures, stromatolite-like structures, and micronodules that are primarily composed of low-crystalline Fe-vernadite and ferrihydrite. Throughout the profiles of MP2D32A, the contents of elements are more or less interdependent. Analysis of elemental correlations from the MP2D32A samples and 847 collected data sets from non-phosphatized hydrogenetic Fe-Mn crusts shows Fe plays a positive role and Mn plays multiple roles in REY accumulation during Fe-Mn crust formation. The REY content increases initially and then decreases with increasing Mn content and Mn/Fe ratio and the turning points (i.e., highest REY contents) mainly occur at an Mn content of ∼18–26% and an Mn/Fe content ratio of ∼0.8. These fundamental results provide novel insights into understanding the influence of Fe and Mn in REY accumulation in the Fe-Mn crusts and are very significant in enhancing our understanding of the REY geochemical processes in the ocean.

Geological and geochemical characteristics of shallow-buried ferromanganese crusts from Weijia Guyot and their resource potential

Numerous buried ferromanganese (Fe-Mn) crusts covered by surface sediments, such as foraminifera ooze, were found on the platforms of certain guyots in the Western Pacific Ocean. To examine the origin of these shallow-buried (<100 cm below the seafloor) Fe-Mn crusts and evaluate their resource potential, we conducted mineralogical and geochemical studies on seven drill cores from the Weijia Guyot(Ita Mai Tai Guyot), which is in the Co-rich Fe-Mn crust contract area of the China Ocean Mineral Resources Research and Development Association (COMRA).The buried Fe-Mn crusts exhibit multilayer structures and are composed of disordered vernadite, similar to the exposed Fe-Mn crusts. Moreover, they show comparable contents of major metallogenic elements (e.g., Mn, Cu, Co, and Ni) and platinum group elements when compared to exposed Fe-Mn crusts. However, they have much higher contents of rare earth elements (REEs) than those of exposed Fe-Mn crusts, indicating a comparable resource potential. The high P contents and collophanite observed in the petrographic microscope indicate that an evident phosphatization event occurred. Based on the tectonic evolution and sedimentation rate, we infer that the phosphatization event mainly took place before the crusts were buried. The phosphatization of shallow-buried Fe-Mn crusts results in an enrichment of REEs and their fractions. This process can also modify the sedimentary environment for Ce precipitation, which may, in turn, alter the diagenetic microenvironment of the shallow-buried Fe-Mn crusts. The mineralogical and geochemical results reveal that burial doesn't cause a significant difference between shallow-buried and exposed Fe-Mn crusts from Weijia Guyot, and they are still of hydrogenetic origin. The findings and research on shallow-buried Fe-Mn crusts indicate that they have comparable resource potentials with exposed Fe-Mn crusts. These results will influence future decisions related to the exploration, exploitation, and utilization of Co-rich Fe-Mn crusts in the contract area of COMRA. Furthermore, it could provide valuable insights for other contractors investigating the platform.