Fe-Mn Crusts Research Articles

Geochemical and mineralogical composition of ferromanganese precipitates from the southern Mariana arc: Evaluation, formation, and implications

The Mariana intraoceanic volcanic arc system in the western Pacific Ocean hosts abundant ferromanganese (Fe-Mn) precipitates. A suite (n = 22) of Fe-Mn precipitates were collected from the southern portion of the arc and their mineralogies and chemical compositions were determined. These results were used to decipher their genetic assemblage, assess their potential as a source of trace metals, and place them into context with respect to Fe-Mn precipitates sampled at higher latitudes in the Mariana arc and from other locations, globally. Minerals identified include vernadite, birnessite, 10 Å manganate, manganite, hematite, goethite, maghemite, calcite, rhodochrosite, quartz, phillipsite, various feldspar, pyroxene, and clay minerals. Element discrimination diagrams indicate that the samples are predominantly of hydrothermal and hydrogenetic-hydrothermal (i.e., mixed) origin, with most reflecting some influence of both. Rare earth element and Y (REY) profiles are distinguished by negative Ce and Y anomalies and positive Eu anomalies. Together, the samples form a continuum from the hydrogenetic to hydrothermal endmembers. Samples with the largest hydrogenetic component are friable with branching oxide/oxyhydroxide growth structures, contain mostly vernadite, and have the greatest concentrations of most metals (including the REY elements). Hydrothermal input produces denser, cemented deposits that contain more 10 Å and 7 Å manganate minerals and lower minor-metal contents. Calculated growth rates range from 6 mm to >190 m Ma−1. Average metal contents of Fe-Mn precipitates from the southern Mariana arc are low relative to hydrogenetic Fe-Mn crusts and hydrothermal Fe-Mn deposits from the northern Mariana arc and elsewhere, globally, and are therefore unlikely to be viable exploration targets.

Microbial Diversity of Deep-Sea Ferromanganese Crust Field in the Rio Grande Rise, Southwestern Atlantic Ocean.

Seamounts are often covered with Fe and Mn oxides, known as ferromanganese (Fe-Mn) crusts. Future mining of these crusts is predicted to have significant effects on biodiversity in mined areas. Although microorganisms have been reported on Fe-Mn crusts, little is known about the role of crusts in shaping microbial communities. Here, we investigated microbial communities based on 16S rRNA gene sequences retrieved from Fe-Mn crusts, coral skeleton, calcarenite, and biofilm at crusts of the Rio Grande Rise (RGR). RGR is a prominent topographic feature in the deep southwestern Atlantic Ocean with Fe-Mn crusts. Our results revealed that crust field of the RGR harbors a usual deep-sea microbiome. No differences were observed on microbial community diversity among Fe-Mn substrates. Bacterial and archaeal groups related to oxidation of nitrogen compounds, such as Nitrospirae, Nitrospinae phyla,Candidatus Nitrosopumilus within Thaumarchaeota group, were present on those substrates. Additionally, we detected abundant assemblages belonging to methane oxidation, i.e., Methylomirabilales (NC10) and SAR324 (Deltaproteobacteria). The chemolithoautotrophs associated with ammonia-oxidizing archaea and nitrite-oxidizing bacteria potentially play an important role as primary producers in the Fe-Mn substrates from RGR. These results provide the first insights into the microbial diversity and potential ecological processes in Fe-Mn substrates from the Atlantic Ocean. This may also support draft regulations for deep-sea mining in the region.

The Nickel isotope composition of the authigenic sink and the diagenetic flux in modern oceans

We investigated Ni isotopes in a stratigraphic sequence of pelagic clays collected during ODP core leg 185 on site 1149 in Western Pacific Ocean near the Izu-Bonin subduction trench in order to determine the Ni isotope composition of the authigenic Mn-oxides sink and evaluate the composition of the diagenetic Ni input flux. This predominant oxic sink likely controls the Ni isotope budget in modern oceans. The sequence presented here is a 170 m-thick sequence of pelagic sediments deposited on some of the oldest oceanic crust of the seafloor, and the base was dated at 104 Ma. Nickel isotope values (δ60/58Ni relative to NIST SRM 986) vary in the range of 0.04 ± 0.04 to 1.03 ± 0.03‰. There is a trend between depth in the stratigraphic sequence and increasing Mn/Fe, Mn/Al, higher Ni concentration and heavier Ni isotope values. This trend is accounted for by authigenic Mn-oxyhdroxides precipitation in the sediment and scavenging of dissolved metals in the sediment porewaters. This indicates that authigenic oxide minerals in deep-sea pelagic clays are a relevant sink for Ni in modern oceans. Results enable us to determine the authigenic oxic output flux of 3.58 × 108 mol/yr of Ni with a Ni isotope composition of 1.2‰, this oxic output is ~0.4‰ lighter than the oxic output flux in FeMn crusts and nodules. This study shows that Ni isotope variations along the stratigraphic sequence could be the result of mixing between a pure pelagic clays end-member at ~0.1‰ and a pure Mn-oxyhydroxides end-member at ~1.2‰. We suggest that to keep the system at steady-state conditions the oxic output flux is compensated for by a diagenetic input flux of 3.7 × 108 mol/yr which is characterized by a highly fractionated Ni isotope composition of ~2.9‰.

Platinum Group Element Geochemistry in Ferromanganese Crust of the Detroit Guyot, Pacific Ocean

Abstract—Hydrogenetic Fe–Mn crusts in the ocean are enriched in platinum but do not accumulate palladium. The mechanism of platinum input into the crusts remains debatable. There is even less data on ruthenium and iridium. In this article, the distribution of platinum group elements (Pd, Ru, Ir, Pt) in ferromanganese crusts of the Detroit guyot (Northwest Pacific) is studied. Based on correlation analyses of major and trace elements, it was shown that accumulation of PGE (Ru, Ir, Pt) occurs from hydrogenetic particulate Fe–Mn oxyhydroxides on all layers with exception of the bottom layer. High platinum contents in the bottom layer are also associated with its input from seawater. However, the most probable additional source of platinum was halmirolysis of underlying basalts.

Nickel isotopes and rare earth elements systematics in marine hydrogenetic and hydrothermal ferromanganese deposits

Attention is now being given to Ni isotope systematics in hydrogenetic marine ferromanganese (Fe-Mn) crusts as paleoceanographic proxies. Previous work focused on identifying both mineralogy (post-depositional) and source effects (Gall et al. 2013; Gueguen et al. 2016), in particular regarding hydrothermal inputs in the oceans and the response of Ni isotope biogeochemical cycling through time. The most important sink for Ni in the oceans is the Fe-Mn oxides sink, but estimation of its Ni isotope composition is only based on hydrogenetic Fe-Mn crusts. In this study, we investigated a range of Fe-Mn deposits including Fe-Mn deposits variably affected by hydrothermal inputs, including hydrothermal deposits from the Lau back-arc basin (South West Pacific) and Lo'ihi seamount (Hawaii), hydrogenetic crust and nodules from the Bauer Basin (Pacific Ocean). Nickel isotope ratios were measured by multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) using a double-spike (61Ni and 62Ni) correction method. The combination of Ni isotopes and rare earth element (REE) geochemistry show that Ni isotope fractionation in Fe-Mn deposits is essentially controlled by formation processes of the deposits (such as the rate of formation, the initial Mn-phase and sorption processes) which are also related to the depositional environment. Consistent with previous studies, pure hydrogenetic crusts are characterized by isotopically heavy Ni isotope signatures (δ60/58Ni values range from ‰ 0.9 and 2.5‰) and well-developed positive Ce anomalies. In contrast, mixed hydrothermal‑hydrogenetic crust and nodules from the Bauer Basin (East Pacific) display negative Ce anomaly and lighter δ60/58Ni values (0.3‰ to 0.4‰), which are interpreted as the result of far-field hydrothermal inputs of Fe-Mn precipitates from the East Pacific Rise.Nickel in hydrothermal deposits from the Lau Basin (0.5 and 1.1‰) and Lo'ihi seamount (−0.8 to −1.5‰) is isotopically lighter than in hydrogenetic Fe-Mn crusts. Light δ60/58Ni values in Lo'ihi deposits is due to the removal of Ni during Ni adsorption from seawater and from the hydrothermal fluid (between 0 and 1.4‰) on Fe-oxides followed by isotope fractionation between the fluid and the mineral phase. Results suggest that Ni isotopes in hydrothermal Fe-rich deposits are strongly fractionated relative to the seawater/fluid source due to partial removal of Ni on Fe-phases. Hydrothermal Mn-oxides deposits from the Lau Basin acquired their Ni isotope signature through Ni adsorption and continuous exchange of Ni with seawater. We propose that the systematic difference in Ni isotope signatures between hydrogeneous and hydrothermal Fe-Mn deposits is related to the mechanisms of Ni uptake into oxide minerals (e.g., birnessite vs. todorokite; Fe-oxides vs. Mn-oxides) which depend on the rate of formation and the source of Mn and Fe to marine ferromanganese deposits (i.e., depositional environment) rather than Ni sources.

Geochemical evidence of Milankovitch cycles in Atlantic Ocean ferromanganese crusts

Hydrogenetic ferromanganese crusts are considered a faithful record of the isotopic composition of seawater influenced by weathering processes of continental masses. Given their ubiquitous presence in all oceans of the planet at depths of 400–7000 meters, they form one of the most well-distributed and accessible records of water-mass mixing and climate. However, their slow accumulation rate and poor age constraints have to date limited their use to explore 100 ka paleoclimatic phenomena. Here it is shown how the Pb isotope signature and major element content of a Fe-Mn crust from the north-east Atlantic responded to changes in the intensity and geographic extent of monsoonal rainfall over West Africa, as controlled by climatic precession during the Paleocene. The studied high-spatial resolution (4 μm) laser-ablation multi-collector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) Pb isotope data is a nearly 2 order of magnitude improvement in spatial and temporal resolution compared to micro-drill subsamples. The record demonstrates cyclicity of the 206Pb/204Pb and 208, 207Pb/206Pb ratios at the scale of single Fe-Mn oxide laminae, in conjunction with variations in the Fe/Mn ratio, Al, Si and Ti content. Time-frequency analysis and astronomical tuning of the Pb isotope data demonstrates the imprint of climatic precession (∼20 ka) modulated by eccentricity (∼100 and 405 ka), yielding growth rates of 1.5–3.5 mm/Ma consistent with previous chemostratigraphic age models. In this context, boreal summer at the perihelion causes stronger insolation over West Africa, resulting in more intense and geographically extended monsoonal rainfalls compared to aphelion boreal summer conditions. This, in turn, influences the balance between the weathering endmembers feeding the north-east Atlantic basin. These results provide a new approach for calibrating Fe-Mn crust records to astronomical solutions, and allow their isotopic and chemical archive to be exploited with an improved temporal resolution of 1000–5000 years.

PALAEOENVIRONMENTAL CONTEXTS FOR MICROBIAL COMMUNITIES FROM Fe-Mn CRUSTS OF MIDDLE-UPPER JURASSIC HARDGROUNDS (BETIC-RIFIAN CORDILLERA)

The Middle-Upper Jurassic transition within the External Subbetic (Betic Cordillera) and the Jbel Moussa Group (Rifian Calcareous Chain) is characterised by numerous stratigraphic breaks recorded as palaeoreliefs, omission surfaces and hardgrounds. One common characteristic is the presence of microbial Fe-Mn crusts and Mn crusts. Three different contexts of microbially mediated Fe-Mn crusts can be distinguished: a) hydrogenetic surficial Fe-Mn crusts and macro-oncoids, b) hydrogenetic cryptic Fe-Mn crusts, and c) hydrothermal surficial Mn crusts. Encrusting foraminifera (Thurammina, Placopsilina, Tolypammina and nubeculariids) and fungi fed on bacteria, while the bacteria and fungi took advantage of the nutrient-rich foraminiferal excretions. The cryptic Fe-Mn crusts are also hydrogenetic crusts developed in the walls of submarine cavities and fractures in the External Subbetic at the time of the hardground development. They are endostromatolites consisting almost exclusively of Frutexites in the case of thin neptunian dykes, or serpulid-Frutexites assemblages in a large neptunian sill. This assemblage reflects the colonization of unfavourable environment (aphotic with low oxygenation) as a response to the photophobic behaviour of chemosynthetic and cryptobiontic microorganisms. Finally, the hydrothermal Mn crusts registered in the Rif are characterised by the record of bacillus-shaped bacteria and different type of filaments. The precipitation of manganese minerals is interpreted as induced by the chemo-organotrophic behaviour of benthic microbial communities, since manganese oxides may form as a result of the direct metabolic activity of bacteria in hydrothermal environments. Very well-preserved fungal hyphae evidence the presence of fungi that probably fed on bacterial communities and their by-products

Isotopic disequilibrium of Cu in marine ferromanganese crusts: Evidence from ab initio predictions of Cu isotope fractionation on sorption to birnessite

In the oceans, Cu is strongly scavenged by ferromanganese (Fe-Mn) crusts. The isotopic fractionation of Cu between seawater and crusts provides insight into the mechanisms of trace metal cycling in the oceans. Dissolved Cu in seawater is isotopically heavy (+0.66±0.19‰) relative to Cu in crusts (+0.31±0.24‰). The primary mineral phase sorbing divalent trace metals in Fe-Mn crusts is birnessite. Recent laboratory measurements show that isotopically light Cu is preferentially sorbed on birnessite, with a fractionation factor of 0.45±0.18‰. Here, we use first-principles (quantum mechanical) calculations to predict the isotopic fractionation between aqueous Cu2+ complexes and Cu as a surface complex on birnessite. We find that isotopic fractionation between the Cu(H2O)5+ complex and sorbed Cu should be 0.49‰ (at 25°C), in close agreement with experiments, confirming that these experimental results reflects equilibrium fractionation. We then predict the isotopic fractionation between dissolved inorganic Cu in seawater and birnessite given the thermodynamic speciation of dissolved Cu at pH 8. We find dissolved inorganic Cu should be 0.94‰ (at 5°C) heavier than Cu sorbed to birnessite. This value is substantially greater than the observed fractionation between seawater and Fe-Mn crusts (Δsw-fmc≈+0.35‰). Moreover, it is well established that dissolved Cu in seawater is strongly complexed by organic ligands. Based on model Cu complexes and published experimental data, we estimate that fractionation of Cu by organic ligands should increase the equilibrium fractionation between seawater and Fe-Mn crusts by 0.2 to 1.5‰ to yield Δsw-fmc = +1.1 to 2.4‰. We conclude that Cu in marine Fe-Mn crusts in not in isotopic equilibrium with dissolved Cu in seawater, and consider the possible explanations of this surprising finding.

Extensive Occurrence of Fe–Mn Crusts and Nodules on Seamounts in the Southern Andaman Sea, India

Extensive Occurrence of Fe–Mn Crusts and Nodules on Seamounts in the Southern Andaman Sea, India

REE Characteristics of Lower Cretaceous Limestone Succession in Gümüşhane, NE Turkey: Implications for Ocean Paleoredox Conditions and Diagenetic Alteration

Trace and rare earth elements (REEs) are considered to be reliable indicators of chemical processes for the evolution of carbonate systems. One of the best examples of ancient carbonate successions (Berdiga Formation) is widely exposed in NE Turkey. The Lower Cretaceous limestone succession of Berdiga Formation may provide a case study that reveals the effect of ocean paleoredox conditions on diagenetic alteration. Measurement of major, trace and REEs was carried out on the Lower Cretaceous limestones of the Berdiga Formation, to reveal proxies for paleoredox conditions and early diagenetic controls on their geochemistry. Studied micritic limestone microfacies (MF-1 to MF-3) indicate deposition in the inner platform to a deep shelf or continental slope paleoenvironment during the Hauterivian-Albian. The studied limestone samples mainly exhibit low Mg-calcite characteristics with the general chemical formula of Ca98.35–99.34Mg0.66–1.65(CO3). They are mostly represented by a diagnostic REE seawater signature including (1) slight LREE depletion relative to the HREEs (ave. 0.72 of Nd/YbN and ave. 0.73 of Pr/YbN), (2) negative Ce anomalies (Ce/Ce* = 0.38–0.81; ave. 0.57), (3) positive La anomaly (La/La* = 0.21–3.02; ave. 1.75) and (4) superchondritic Y/Ho (ave. 46.26). Studied micritic limestones have predominantly low Hf (bdl to 0.5 µg/g), Sc (bdl to 2 µg/g) Th (bdl to 0.9 µg/g) contents suggesting negligible to minor shale contamination. These findings imply that micritic limestones faithfully record chemical signals of their parental and diagenetic fluids. The succession also exhibits high ratios of Eu/Eu* (1.01–1.65; ave. 1.29 corresponding to the positive Eu anomalies), Sm/Yb (1.26–2.74; ave. 1.68) and La/Yb ratios (0.68–1.35; ave. 0.9) compared to modern seawater and wide range of Y/Ho ratios (29.33–70.00; ave. 46.26) which are between seawater and hydrogenetic Fe-Mn crusts. Several lines of geochemical evidence suggest water-rock interaction between parental seawater and basaltic rocks at elevated temperatures triggered by hydrothermal activity associated with Early Cretaceous basaltic magma generation. The range of Ce/Ce* values is suggestive of mostly oxic to dysoxic paleoceanographic conditions, with a sudden change to dysoxic conditions (Ce/Ce* = 0.71–0.81), in the uppermost part of the MF-1. This is followed by an abrupt deepening paleoenvironment with a relative increase in the oxic state of the seawater and deposition of deeper water sediments (MF-2 and MF-3) above a sharp transition. The differences in microfacies characteristics and foraminifera assemblage between MF-1 and overlying facies (MF-2 and MF-3) may also confirm the change in paleoceanographic conditions. Therefore, REEs data obtained from studied limestones have the potential to contribute important information as to regional paleoceanographic conditions of Tethys during an important period in Earth history.

Towards balancing the oceanic Ni budget

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 (δ60NiNIST 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 0.6−2.3×108 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.

Changes in sediment source areas to the Amerasia Basin, Arctic Ocean, over the past 5.5 million years based on radiogenic isotopes (Sr, Nd, Pb) of detritus from ferromanganese crusts

Ferromanganese (FeMn) crusts provide a useful paleoenvironmental archive for studying the poorly understood climatic, oceanographic, and geologic evolution of the Arctic Ocean. This study is based on the identification and temporal reconstruction of sources and inferred transport pathways of terrigenous material in FeMn crusts collected from several sites across the Amerasia Basin. Samples from the Alpha Ridge (AR), Mendeleev Ridge (MR), and Chukchi Borderland (CB) have similar chemical compositions and high detrital contents. Sr, Nd, and Pb isotopic compositions of the terrigenous detritus extracted from the FeMn crust layers show spatial and temporal variability due to the variable proportions of inputs from the North American and East Siberian margins and local submarine outcrops. The temporal resolution is restricted by macroscopic crust layers, which represent times of significant changes in the depositional environment and are used to study first-order environmental changes. During the period of ca. 4.4 to 3.8 Myr ago, detritus in the MR area was derived mostly from the Laptev Sea. Then, until about 1.3 Myr ago, FeMn crusts from MR received a higher volcanic component sourced from the East Siberian Sea, with mixing of detritus from the Okhotsk-Chukotka volcanic belt (OCVB) area and possibly weathering of local MR outcrops, which is mostly High Arctic Large Igneous Province (HALIP) rocks. The period from about 1.3 Myr ago to the present reflects enhanced contributions of detritus from the Canadian Shield, approximately equal to the East Siberian contribution for the MR area. CB crusts show three main periods of distinct detrital input. During the period ca. 5.5–5.0 Myr ago, CB detritus was sourced from local submarine outcrops of the Jurassic-Cretaceous HALIP rocks and possibly from northeast Siberia, including OCVB rocks, while during the period from about 5.0 to 3.6 Myr ago, the CB FeMn crusts had a much greater input of detritus from the North American margin. After 3.6 Myr ago, the CB detritus shows a mixed composition predominantly sourced from North America with some material transported from the Bering Sea and smaller contributions from northeast Siberia. The AR crust was influenced mostly by detritus sourced from the Canadian Shield.This study shows that FeMn crusts from the Arctic ocean are a useful tool and archive for climate reconstruction and depositional history of this polar region.

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

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.

Variabilities and enrichment mechanisms of the dispersed elements in marine Fe–Mn deposits from the Pacific Ocean

The eight elements Ga, Ge, Se, Cd, In, Te, Re and Tl are usually referred to as “dispersed elements”, and they have a lower average abundance in the Earth’s crust. Marine Fe–Mn crusts and nodules are potential resources for many of the metals used in emerging high- and green-technology applications. This study examines the concentrations of the dispersed elements in marine Fe–Mn deposits at different locations from the Pacific Ocean, ascertains the genesis and dispersed elements enrichment characteristics of marine Fe-Mn deposits, discusses the variations of the dispersed elements in marine Fe–Mn deposits profiles and variations with the dependency of genesis and water depth, and elucidates their incorporation mechanisms in marine Fe–Mn deposits. Nodules from the Mid-Pacific Mountains (CAD19 and CXD05) and Magellan Seamounts (MID18) formed under hydrogenetic conditions, nodules from the CCZ (WD1101, WT0301 and ET0301) formed under a mixture of hydrogenetic and diagenetic conditions, and the Fe–Mn crust MKD12 from the Magellan Seamounts formed under hydrogenetic condition throughout its growth history. Compared with the Earth’s crust and the pelagic clay, the marine Fe–Mn deposits are highly enriched in Te, Tl, Se and Cd, not enriched in Re, Ga, Ge, In. Elemental relationships show that there are distinct differences between the enrichment mechanisms of the dispersed elements in different types of Fe–Mn deposits. Cd, Se, Te and Tl in Fe-Mn nodules and crust profiles show certain regular variations, which mainly related to the changes of the relative contents of Mn minerals and Fe minerals, for the phosphatized crusts, the concentrations of dispersed elements would be influenced by phosphatization. There are obvious differences of Cd, Se, Te and Tl concentrations in different genetic types of Fe–Mn deposits, which probably attributed to the differences of sources, deposition rates and mineral compositions. The concentrations of Se, Cd, Te and Tl in Fe-Mn deposits from the Pacific Ocean mainly distribute in the ranges of 1000 ~ 2500 m and 4000 ~ 6000 m water depth. The water depth dependence of Se, Cd, Te and Tl concentrations in hydrogenetic Fe-Mn nodules and crusts display different variation patterns, which might be controlled by several factors such as the Mn-phase and Fe-phase system, sedimentation rates, biological productivity, diagenesis, as well as the geochemical behaviors of the elements themselves. Under the conditions of hydrogenetic and hydrogenetic-diagenetic, Cd, Se, Te and Tl are incorporated in marine Fe-Mn deposits mainly by adsorption onto the Mn-oxide or/and Fe oxyhydroxide particles. The processes of coupled redox and coprecipitation on Fe-Mn(oxyhydr)oxides could generate Te enrichment.

Seabed Mapping Using Shipboard Multibeam Acoustic Data for Assessing the Spatial Distribution of Ferromanganese Crusts on Seamounts in the Western Pacific

Cobalt-rich ferromanganese crusts (Fe–Mn crusts), potential economic resources for cobalt, nickel, platinum, and other rare metals, are distributed on the surface of seamounts, ridges, and plateaus. Distribution of Fe–Mn crust deposits and their geomorphological characteristics are prerequisites to selecting possible mining sites and to predicting the environmental impact of deep-sea mining activity. Here, we map the spatial distribution of Fe–Mn crust deposits on seamount summits and flanks in the Western Pacific using shipboard multibeam echo sounder (MBES) data and seafloor images from a deep-towed camera system (DCS) and evaluate the relationship between acoustic backscatter variations and the occurrence of Fe–Mn crusts. We find a positive correlation between high backscatter intensity, steep seabed slope gradients, and the occurrence of Fe–Mn crusts. However, our analysis was not effective to distinguish the spatial boundary between several seabed types that occur over small areas in mixed seabed zones, particularly where transition zones and discontinuous seabed types are present. Thus, we conclude that MBES data can be a valuable tool for constraining spatial distribution of Fe–Mn crust deposits over a large exploration area.

Geographic and Oceanographic Influences on Ferromanganese Crust Composition Along a Pacific Ocean Meridional Transect, 14 N to 14S

AbstractThe major controls on the variability of ferromanganese (FeMn) crust composition have been generally described over the past 40 years; however, most compilation studies lack quantitative statistics and are limited to a small region of several seamounts or compare FeMn crusts from disparate areas of the global oceans. This study provides the first detailed research to address the geographic and oceanographic controls of FeMn crust composition from a line of seamounts across 30° of latitude in the west central Pacific. Element concentrations from the uppermost layer (<15 mm) of 57 FeMn crusts were evaluated for statistically significant variance and correlation with a variety of oceanographic and geographic parameters. Manganese, Co, Ni, Mo, and Zn concentrations in crusts in this region are highly anticorrelated with seawater oxygen concentrations, suggesting oxygen as the dominant controlling factor for these elements. Iron instead correlates with water depth, which we attribute to increased carbonate ion concentration with increasing water depth. Silicon and Al content in crusts demonstrate a potential meridional variance of detrital inputs and sources in the region. Iron, Ba, and Mg are enriched in FeMn crusts below the equatorial upwelling zone which is related to biological productivity. Fluctuations in the four oceanographic and geographic parameters, seawater oxygen content, detrital input, surface productivity, and deep sources of iron, are robustly recorded by FeMn crusts. Modern measurements of these primary parameters, as well as paleoceanographic reconstructions, can be used to define regions of interest for FeMn crust exploration.

Potential mineral resources of the Chilean offshore: an overview

The seabed included in the Chilean Exclusive Economic Zone (EEZ) has proper conditions to originate and host different ore deposits, but its geological knowledge is scarce and scattered. The existent studies are very limited in terms of geochemical and mineralogical analyses. The most significant non-energetic mineral resources off Chile correspond to Fe-Mn nodules and crusts, phosphorite deposits, gold and titanium placer deposits and massive sulfide deposits. Fe-Mn nodule sites occur in abyssal plains and seamounts, and around volcanic islands, at depths from 2,890 to 4,332 m, and can contain important concentrations of Cu and Ni (up to 1.38% Cu+Ni) and Co (up to 0.53%). Co-rich Fe-Mn crust occurrences have been reported around the Rapanui and Salas y Gómez islands, with Cu+Ni contents up to 0.3%. Phosphorite sites occur in Holocene sedimentary beds of the continental shelf off Peru and northern Chile, with P2O5 average content of 22.6%. Gold placer deposits are found in beaches and channels of southern Chile and may extend offshore probably in submarine canyons. Titanium placer deposits have been evaluated in different beaches of Chile and could also be continued offshore. Platinum anomalies have been found in channels and bays of southernmost Chile. No samples of Volcanogenic Massive Sulfide (VMS) mineralization are known in the Chilean EEZ to date. However, samples of hydrothermal vents, with potential for polymetallic VMS type mineralization, have been recovered around the Rapanui Island, and several seamount and volcanic island chains indicate favorable conditions for formation and preservation of these ore-deposits. The available geological information on the seabed of the Chilean EEZ is insufficient to estimate the real potential of its non-energetic mineral resources.

Geochemistry and origins of carbonate fluorapatite in seamount Fe[sbnd]Mn crusts from the Pacific Ocean

Seamount phosphates are increasingly regarded as potential resources for rare earth elements (REE) and plus yttrium (REY). Carbonate fluorapatite (CFA) formed within seamount ferromanganese (FeMn) crusts is the most common seamount phosphate mineral. However, reports on the mineralogy and geochemistry of CFA are few and thus its origin and acquisition of trace elements are not well understood. In this study, we analyzed the major and trace elements of CFA in FeMn crusts collected from Western and Central Pacific seamounts to investigate the genesis of trace elements in the CFA. This is the first study to use in situ analytical techniques such as electron microprobe analyzer (EPMA) and laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) to analyze seamount CFA. We found that the CFA hosts abundant minor and trace elements and propose that ionic substitutions are responsible for the high contents of SO3, SiO2, REY, Sr, Na, Fe, and Mn in the CFA veins found in the FeMn crusts, i.e., SiO32− and SO42− substitute for PO42−, while REE3+, Y3+, Na+, Fe2+, and Mn2+ substitute for Ca2+. REE3+ substitutions for Ca2+ in the CFA are charge-compensated by Na+ substitution for Ca2+. Fourier transform infrared spectroscopy (FTIR) analysis shows that CO32– mainly substitutes for PO42− in the CFA crystal structure, and there is a minor substitution of PO42− by CO3F3−. Ocean water is the major source of the P and REY, which when precipitated as seamount CFA is characterized by high ∑REE (345 to 6016ppm) and heavy-REE (HREE) enrichments. Monazite grains dispersed in the seamount CFA contribute trace amount of REY. These results shed light on the composition and element mobility of seamount CFA with economic potential, which also provides valuable insights into global ocean chemical cycling (e.g. REE).

Accumulation of ferromanganese crusts derived from carrier-free 10Be/9Be

The occurrence of 10Be in natural archives is commonly used to date their formation and growth on time scales of million years. Accelerator Mass Spectrometry (AMS) can perform a direct measurement of the 10Be/9Be ratio. The carrier-free method, in which no 9Be carrier is added to the original sample, is especially suitable for 10Be/9Be ratio determination in the marine environment. By normalizing the 10Be content to 9Be, temporal variations of Be uptake processes into the archive are eliminated.Here, we present a simple method for the chemical extraction of beryllium from ferromanganese (FeMn) crusts or nodules, the measurement procedure, and the first carrier-free 10Be/9Be measurements at the 3 MV AMS facility VERA. Several tests of chemical methods are discussed including different options to short-cut and accelerate the procedure for special cases. Results from FeMn crust 237KD from cruise VA13/2 in the Pacific ocean show the known 10Be/9Be distribution with depth that is commonly related to a changing growth rate of the archive. In this context we discuss the potential influence of diffusion and adsorption processes on the age models of FeMn crusts that are based on radioactive nuclides such as 10Be and 230Th. Including an open-system behavior for these isotopes in the description of their profiles allows interpreting the accumulation of crusts with a constant growth rate over millions of years and does not require the assumption of abrupt growth changes.

Late Cretaceous and Cenozoic paleoceanography from north-east Atlantic ferromanganese crust microstratigraphy

Oceanic hydrogenetic ferromanganese (Fe-Mn) crusts precipitate directly from ambient seawater over millions of years. Their very slow growth rates and physio-chemical properties mean that they adsorb numerous elements from seawater. As such, they provide condensed records of seawater evolution through time that can be used for paleoceanographic reconstruction. Here, we present the results of a high-resolution, stratigraphic, textural and geochemical investigation of a core sample, obtained from a Fe-Mn crust pavement, located on the summit of Tropic Seamount in the tropical north-east Atlantic Ocean. A number of observations and interpretations are proposed, within the context of a well-constrained age model, spanning the last 75 ± 2 Myr. This core has textural stratigraphic coherence with Pacific Fe-Mn crusts formed since the Late Cretaceous, highlighting that global oceanic and climatic phenomena exert first-order controls on Fe-Mn crust development. All major hiatuses observed in the Fe-Mn crusts are contemporaneous with erosion events occurring throughout the Atlantic Ocean. High-resolution geochemical data indicate that there is variability in the composition of Fe-Mn crusts at the cm to μm scale. The dominant factors controlling this include major oceanographic events, mineral textures and micro-topography.