Hydrogenetic Ferromanganese Crusts Research Articles

Magnetic and geochemical scanning reveals growth history of marine ferromanganese crust on Detroit Seamount, northwest Pacific since the early Miocene

The Hawaiian Chain-Emperor Seamounts is known to be one of the most active regions influenced by mantle hotspot. However, previous studies have provided limited information on the growth process and metal enrichment of marine ferromanganese crusts as indicators of post-eruption history. In this study, we conducted a geochronological and major elemental study of a hydrogenetic ferromanganese crust, from the Detroit Seamount using high-resolution magnetic and geochemical scanning. Our findings are as follows: (1) A total of 39 magnetozones are recognized in the studied section of the crust, which can be preliminarily correlated to the geomagnetic polarity timescale from chrons C1n to C5Dn. This correlation yields growth rates of 1.48–2.18 mm/Myr over the past ∼18 Myr. (2) Columnar and lamellar growth structures are identified with distinct metal enrichment patterns. A significant transition from lamellar to columnar growth occurred at ∼11.6 Ma. (3) The quantified elements can be clustered into three groups, (Mn, Cu–Co–Ni, and Al–Si), (Fe and Ti), and Ca. A strong correlation between metal enrichment in the crust and the global benthic foraminifera δ13C record is then observed. Based on these results, we suggest a predominant role of deep-sea redox conditions in the growth history of ferromanganese deposits on the Detroit Seamount since the Early Miocene.

Stable chromium isotope compositions of hydrogenetic ferromanganese crusts potentially linked to primary productivity

Stable chromium isotope composition (δ53Cr) is a widely used paleo-redox proxy. However, modern seawater δ53Cr values do not correlate with dissolved O2 concentrations, suggesting that non-O2 factors may influence marine Cr cycling. We present new δ53Cr data for two hydrogenetic ferromanganese (FeMn) crusts deposited in the western- and central-north Pacific Ocean since the late Eocene, a period when the ocean remained largely oxic. Simple isotope mass balance and Rayleigh distillation models suggest that trivalent Cr is likely the major Cr species incorporated from seawater into the Fe phases of hydrogenetic FeMn crusts. The δ53Cr values of FeMn crusts decrease from −0.35‰ in the late Eocene to −0.74‰ in the middle Miocene, followed by increasing to modern values ranging from −0.33 to −0.47‰. The temporal trend of δ53Cr follows that of the regional pelagic sedimentation rate, suggesting that primary productivity may have played a role in shaping the δ53Cr signals recorded in the hydrogenetic FeMn crusts. Our data show that non-O2 factors may influence δ53Cr values recorded in Fe-rich sedimentary archives deposited in a largely oxic ocean, thus adding more complexities to the Cr isotope paleoproxy.

Thorium isotope evidence for glacial–interglacial dust storminess and productivity in the North Pacific gyre

The flux of dust deposition to the ocean and its impact on marine biological productivity are outstanding issues of the Earth’s climate system. The North Pacific gyre (NPG) is the Earth’s largest ecosystem and is important for marine nitrogen fixation, which is sensitive to Asian dust-regulated surface nutrient stoichiometry. Meanwhile, it is one of the least studied regions in the global ocean during the late Pleistocene, because of the extremely slow sediment accumulation and lack of biological material preservation. 232Th and 230Th concentrations recorded by hydrogenetic ferromanganese crusts in the deep NPG provide a novel and quantitative proxy of dust deposition and export productivity in this region. For this purpose, we have established an in situ U–Th isotope analytical technique on hydrogenetic ferromanganese crusts collected from the deep NPG. Iron, Mn, and Co of our samples have also been analyzed to constrain the impact of dust dissolution on the Fe geochemical cycle. Remarkably, variability of the 232Th-based dust flux over the last ∼900 ky exhibits a striking resemblance to grain-size records of the Chinese loess deposits and sea-level reconstructions but clearly decouples from the global temperature evolution. On orbital time scales, dust storms over the NPG are apparently sensitive to effects related to continental ice sheet sizes but decoupled from major global cooling during the early glaciation. While our 232Th data indicate a 2- to 3-fold variability of glacial–interglacial dust flux, scavenging of Fe, Mn, and Co in the deep NPG is much less variable through the late Pleistocene. We suggest that variable dust fluxes have a limited impact on the inventory of dissolved Fe in the deep waters of NPG, even though the scavenging of Fe has likely been regulated by glacial–interglacial paleoceanography. The paired 230Th-scavenging-based biological productivity tracks gyre sea surface temperature rather than dust flux during the last glacial cycle. We observe no correlation between dust flux and export productivity in the NPG, indicating that dust-derived Fe is not the productivity-limiting factor on orbital time scales in this region. Instead, these results imply that changes in gyre mixing and mode water formation might have led to increased supply of phosphorous and thus enhanced glacial biological carbon sequestration, with potentially stronger nitrogen fixation under higher eolian input.

Microstratigraphic evidence of oceanographic and tectonic controls on hydrogenetic ferromanganese crusts in the NW Pacific seamounts

Selected hydrogenetic ferromanganese crusts were characterized at a microstratigraphic scale across various NW Pacific seamounts. The crusts encompassed over 100 sites, and were mostly found on old rock outcrops. The crusts also exhibit spatial compositional variation and are largely enriched in Co and Ni. However, the parameters controlling this compositional variation remain unclear. To address this issue, we characterized the microstructure, mineralogical and chemical compositions of seven carefully selected samples from topographic highs in the mid-latitudes on the Philippine Sea and Pacific plates and revealed the following trends: (1) the lower phosphatized layer formed in the middle Miocene or earlier and only on the Pacific Plate, (2) an increasing Co/Mn ratio with younger age from the substrate to the surface, and generally higher in the Pacific Plate than the Philippine Sea Plate, and (3) an increase of detrital quartz and plagioclase since approximately 5 Ma, with high Al/Mn ratios near the continental margin and to a lesser extent in pelagic areas. These results are partly congruent with those of other sediment cores from the other NW Pacific basins. Furthermore, the secular increase of Co and detrital minerals in the crust samples suggests a strong influence of oceanographic and tectonic conditions, especially the expansion of the oxygen minimum zone (OMZ) for the former and a significant input of detrital materials from the continents for the latter.

Fractionation of germanium and silicon during scavenging from seawater by marine Fe (oxy)hydroxides: Evidence from hydrogenetic ferromanganese crusts and nodules

Germanium (Ge) and silicon (Si) are an element pair which shows rather coherent behaviour in many geochemical systems. In aqueous systems and in the critical zone, however, Ge and Si may fractionate from each other, leading to slight differences between the Ge/Si ratios of continental crust, river water and seawater. We here show that even stronger fractionation of the GeSi couple occurs within seawater during the formation of hydrogenetic ferromanganese (FeMn) crusts and nodules. We determined Ge/Si ratios of hydrogenetic FeMn crusts from the Pacific Ocean following a new analytical approach using laser-ablation ICP-MS on nano-particulate tablets prepared from the FeMn crust material. Data quality was monitored and demonstrated by repetitive measurements of FeMn nodule reference material (RM) NOD-P1 from the Pacific Ocean (Ge/Siwt: 16.8 × 10−6 g/g; Ge/Simol: 6.47 × 10−6 mol/mol), which is the only RM for which high-quality GeSi reference data are available. We also report Ge/Si ratios for FeMn nodule RMs NOD-A1 from the Atlantic Ocean (Ge/Siwt: 24.9 × 10−6; Ge/Simol: 9.6 × 10−6) and for JMn-1 from the Pacific Ocean (Ge/Siwt: 17.9 × 10−6; Ge/Simol: 6.9 × 10−6). The Ge/Siwt ratios of the hydrogenetic FeMn crusts from the Pacific Ocean range from 13.2 × 10−6 to 33.5 × 10−6 (Ge/Simol: 5.1 × 10−6 to 13 × 10−6). The Ge/Si ratios of both FeMn crusts and nodules are significantly higher than those of ambient seawater (ca. Ge/Siwt: 1.7 × 10−6; Ge/Simol: 0.7 × 10−6). Their Ge/Si ratios are also well-above those of potential (alumino)silicate detritus. Hence, these high Ge/Si ratios reveal fractionation of Ge and Si during scavenging from seawater by the iron (oxy)hydroxide component in FeMn crusts, and do not result from the presence of detrital material in the chemical precipitate. Their high Ge/Si ratios relative to seawater also suggest that despite higher complexation constants with organic ligands for Ge than Si, dissolved organic ligands do not control marine GeSi fractionation via preferential retention of Ge in seawater.

Gold in Ferromanganese Deposits from the NW Pacific

Ferromanganese crusts from four different areas of the North-West Pacific Ocean—the Detroit (northern part of the Imperial Ridge) guyot, the Zubov (Marshall Islands) guyot, the “Gummi Bear” seamount (an intraplate volcano near the Krusenstern FZ), and Belyaevsky volcano (the Sea of Japan)—were studied. Samples from the Detroit and Zubov guyots and the “Gummi Bear” seamount have similar chemical and mineral compositions of hydrogenetic cobalt-rich ferromanganese crusts. Crust from the Sea of Japan seems to reflect a hydrothermal influence. The gold content in most samples from the Detroit guyot was 68 ppb and from the Zubov guyot varied from 180 to 1390 ppb, which is higher than the average for the Pacific crusts (55 ppb). Gold content in two other samples was less than 10 ppb. Based on the electron microscopic studies, aggregation of gold particles with a size of 680 μm were identified in the Detroit guyot crust. The sizes of the Au particles are up to 10–15 μm, which has not been previously noted. Gold particles similar in morphology and size were also found in the Zubov guyot crust, which is located far from the Detroit guyot. The largest particle of gold (≈60 μm), represented by electrum, was found in the clay substrate from the “Gummi Bear” seamount. The lamellar, rudaceous morphology of the gold particles from the Detroit and Zubov guyots reflects their in situ formation, in contrast to the agglutinated, rounded with traces of dragging gold grain found in the substrate of the sample from the “Gummi Bear” seamount. Three-component (Ag-Au-Cu) gold particles were found in the hydrothermal crust from the Belyaevsky underwater volcano. Grains similar in composition were also found in Co-rich crust. The research results show that the gold was probably added to by hydrothermal fluid in the already-formed hydrogenetic ferromanganese crusts during rejuvenated volcanic stages. Biogeochemical processes may have played a major role in the formation of submicron solid-phase gold particles.

Controls on metal enrichment in ferromanganese crusts: Temporal changes in oceanic metal flux or phosphatisation?

Oceanic hydrogenetic ferromanganese (Fe-Mn) crusts are a major repository for many metals, such as Co, Ni, Cu, Pt, Te and REE, which are essential for decarbonisation of transport and energy systems. Secondary mineralisation processes, occurring during phosphatisation episodes, commonly impregnate the shallower deposits with carbonate fluorapatite (CFA). The suboxic oceanic conditions during such events are frequently invoked to explain the lower Co content and unusually high Ni, Cu, Zn and Pt content of older phosphatised crusts. Here, the hypothesis of suboxic diagenetic recrystallization induced by phosphatisation episodes as a driving mechanism for Ni, Cu, Zn and Pt enrichment and Co depletion is evaluated. Accurately dated geochemical profiles, spanning 75 Ma of depositional history, for a shallow (1100 mbsl) phosphatised sample and a deeper (3100 mbsl) unphosphatised sample from Tropic Seamount in the north-east Atlantic, are compared. An isocon analysis, which allows to quantitively evaluate chemical gains and losses in mass transfer and therefore permits compensation for the dilution effect induced by the addition of CFA in the Fe-Mn crusts, demonstrates that no loss of Co has occurred in the phosphatised crust, whilst Pt, Te, Cu, Ni and Zn are enriched relative to younger, unphosphatised Fe-Mn crust. Both geochemical profiles show sympathetic trends and similar amplitudes of variation in concentration. This excludes phosphatisation as the driving mechanism for the metal enrichment and depletion. Systematic differences in metal content between the two samples, such as higher Cu and lower Co content in the deeper sample, are consistent with the depth profile of dissolved metal concentrations in the water column. The variability observed in the geochemical profiles is consistent with temporal changes in metal fluxes to the ocean, as a result of the evolving climate and oceanographic configuration of the north-east Atlantic Ocean through the Cenozoic. It is concluded that changing metal fluxes, rather than secondary mineralisation process associated with phosphatisation, is the dominant control on the primary metal content in Fe-Mn crust deposits at Tropic Seamount.

Gallium-aluminum systematics of marine hydrogenetic ferromanganese crusts: Inter-oceanic differences and fractionation during scavenging

Despite its status as a critical metal in the EU and the U.S., the geochemical behavior of gallium (Ga) in the Earth’s surface environment is not yet well constrained, which is in marked contrast to its geochemical partner aluminum (Al). Especially hydrogenetic ferromanganese crusts which may represent a potential future unconventional resource of critical metals, are surprisingly underexplored with regard to their Ga-Al systematics. This study presents the first data on the Ga-Al pair in hydrogenetic Fe-Mn crusts from various locations in the Pacific Ocean and from the Rio Grande Rise in the SW Atlantic. We also provide Ga-Al data for certified reference materials for Fe-Mn nodules NOD-P-1, NOD-A-1, and JMn-1. Our results also show that marine hydrogenetic Fe-Mn crusts cannot be considered an unconventional Ga resource, in marked contrast to several other critical metals.Aluminum and Ga concentrations in these precipitates are not controlled by detrital components. Both elements show a geochemical behavior comparable to that of the hydroxide-dominated elements Zr and Hf during scavenging from ambient seawater by hydrogenetic Fe-Mn crusts. The Ga/Al mass ratios of Atlantic (0.10–0.16 g/kg) and Pacific crusts (0.18–1.2 g/kg) are about one and a half orders of magnitude lower than those of respective ambient seawater and mimic the inter-oceanic fractionation of the Ga-Al pair between these two ocean basins. Without exception, the Atlantic Fe-Mn crusts show lower Ga/Al ratios than the Pacific crusts. The systematically lower Ga/Al ratios of the crusts relative to those of seawater reveal preferential scavenging of Al relative to Ga during the formation of Fe-Mn crusts. This is in line with previous studies that reported a higher particle reactivity of Al compared to Ga in the marine environment. However, this fractionation trend contradicts predictions based on a simplified model commonly used to approximate trace element scavenging by marine metal (hydr)oxides based on hydrolysis constants, which favors Ga enrichment relative to Al as the hydrolysis constant of Ga is higher than that of Al. The observed Ga-Al fractionation may be related to the preferential retention of Al compared to Ga on the surface of the Fe-Mn (oxyhydr)oxides because in contrast to Ga, desorption of Al is characterized by very slow reaction kinetics or is even irreversible. Alternatively, stronger organic complexation of dissolved Ga than Al in seawater (which is supported by the stability constants of various organic Ga and Al complexes) and the resulting preferential retention of Ga over Al in solution by dissolved organic ligands may be another viable mechanism to explain the observed Ga-Al fractionation between hydrogenetic Fe-Mn crusts and seawater. While more experimentally determined thermodynamic data are necessary, the rather consistent difference between hydrogenetic Fe-Mn crusts and ambient seawater supports an important role of organic ligands in the chemical speciation of Ga in seawater.

Regional and fine-scale variability in composition and structure of hydrogenetic ferromanganese crusts: Geological characterization of 25 drill cores from the Marcus-Wake seamounts

Hydrogenetic ferromanganese crusts in the northwestern (NW) Pacific seamounts are considered as potential future sources of strategic metals. The details of their regional and fine-scale variations in composition and structure are currently unknown. We attempted to characterize the variation patterns in a selected area of the NW Pacific seamounts, based on geological and geochemical analyses, which were performed with a TV-monitored drill machine and remotely operated vehicles, after full bathymetric mapping and an acoustic survey. Subsequent chemical, mineralogical, and structural analyses of the well-preserved crust cores indicated that the hydrogenetic crusts in the seamount area have similar distinct fine-scale variations throughout the growth layers from the substrate to the surface. The crust cores show almost continuous stratigraphic growth since the middle Miocene (approximately 15 Ma ago) or earlier, with significant variations in metal concentration, growth structure, and mineralogy. The fine-scale stratigraphic variations are surprisingly well-correlated across the seamount areas of approximately 1000 km apart; thus, the bulk compositional variation becomes much smaller than a secular variation when compared within the seamount area. Stratigraphic analysis is crucial for the compositional characterization of ferromanganese crusts on various scales.

Banded iron formation from Antarctica: The 2.5 Ga old Mt. Ruker BIF and the antiquity of lanthanide tetrad effect and super-chondritic Y/Ho ratio in seawater

Here we report the first detailed geochemical data for Banded Iron-Formation (BIF) from Antarctica. Micro drill cores were taken from adjacent magnetite/haematite and metachert bands from the 2.5 Ga old Mt. Ruker BIF, Prince Charles Mountains, East Antarctica. Low concentrations of Al, Zr, Hf, and Sc reveal the purity of the samples. The chemical composition matches closely that of other early Precambrian BIF, except for an enrichment of Ni, and high Ba/Sr ratios in the metachert. Shale-normalized Rare Earths and Yttrium (REYSN) patterns show all the features of modern seawater such as depletion of light vs heavy REYSN, positive anomalies of LaSN, GdSN, and YSN (i.e. super-chondritic Y/Ho ratios) and the W-type lanthanide tetrad effect (LTE), but positive EuSN and no CeSN anomalies (and no positive Eu anomalies in chondrite-normalized REY patterns). This distribution is fully compatible with that of other pure Early Precambrian BIFs, suggesting high-temperature hydrothermal input of REY into seawater and a redox level of the atmosphere-hydrosphere system too reducing for Ce oxidation. The uniform, super-chondritic Y/Ho ratios in adjacent iron-oxide and metachert BIF bands most strongly suggest that the conspicuous banding does not result from post-depositional separation of an initially homogenous Fe-silicate precipitate, but argues for a primary origin of the banding. The super-chondritic Y/Ho ratios fit well within the range reported for other BIF worldwide, corroborating that positive Y anomalies, although possibly of smaller size than today, have always been a characteristic feature of seawater. The Mt. Ruker BIF further complements the set of Early Precambrian marine chemical sediments in which the W-type LTE has been observed, and demonstrates the antiquity of the LTE in seawater. These subtle features reveal that the distribution of the redox-insensitive REY in seawater did not change significantly over the almost 4 billion years geological record of seawater. The super-chondritic Y/Ho ratios and W-type LTE in this and other oxide-facies BIF are in marked contrast to the REY distribution in Modern and Cenozoic oxidic hydrogenetic ferromanganese crusts, pointing towards fundamentally different removal mechanisms of REY from Modern vs Early Precambrian seawater.

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.

Modern precipitation of hydrogenetic ferromanganese minerals during on-site 15-year exposure tests

Redox-sensitive metallic elements, Mn and Fe, are oxidized in deep sea waters and form abundant ferromanganese crusts and nodules on the world’s ocean floors at ultraslow rates of growth. This process of oxidation and the mechanism of precipitation are yet unknown. In this paper, the results of the first successful, long-term, on-site experiment of mineral precipitation that ascertains modern, ongoing hydrogenetic deposition of oxide materials from normal seawaters at water depths of 900–4500 m of geologically active and inactive environments are presented. We succeeded in the in-situ precipitation experiment on the sea floor and characterized the precipitates using high-resolution and submicron-scale chemical, mineralogical, and structural analyses. The installed artificial plates of glass, ceramics, and plastic yielded spread-out particles of sizes varying from one to a few micrometers in diameter, of coccoid-like irregular shapes, with a maximum of 1,000–10,000 individual particles/mm2/year after 12–15 years of exposure. The results indicated a continuous substantial growth of the hydrogenetic minerals if both Mn and Fe are supplied to the bottom waters. The mineralogical, chemical, and structural properties of the precipitates are similar to those of the natural precipitates on the seabed that are made up of hydrogenetic ferromanganese crusts and nodules, together with settling sediments, suspended hydrothermal particles, or microbial precipitates from cultivated Mn-oxidizing bacteria. Our work presents new realistic insight into proposed genetic models of marine hydrogenetic ferromanganese deposits in modern diverse ocean environments.

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.

Distribution of and hydrographic controls on ferromanganese crusts: Tropic Seamount, Atlantic

Hydrogenetic ferromanganese crusts are likely to be exploited as resources for critical metals in the near future, yet the processes controlling where and how they grow are poorly understood. Using detailed mapping of seafloor outcrop and well constrained hydrographic modelling alongside scanning electron microscope imagery of samples from the Tropic Seamount, a star-shaped guyot located in the Tropical East Atlantic, we investigate the relationship between currents, ferromanganese crustal texture and the locations and intensity of crustal erosion. Here, we report the distribution of FeMn crusts and explore factors controlling their growth and erosion. We find that just over 35% of the summit plateau of the guyot exposes some form of ferromanganese crust mineralisation, with the rest variably covered by plains of mobile sediment and slim cliff exposures of carbonate. The steep flanks of the guyot largely expose ferromanganese crust both in situ and as debris flows. The strongest currents are located on the upper flanks of the guyot, the central part of its eastern limb, and across the summit plateau. Three categories of surface morphologies are identified; from pristine botryoidal surfaces to flat areas that have been completely polished by the erosive action of currents and sediment. The relationship between the outcrop of crusts, their erosional states and the hydrographic current regime to which they are exposed is complicated. There is a general correlation between the degree of erosion and location across the seamount, with the least eroded being found on the flanks below 2000 m water depth and the most heavily eroded crusts largely restricted to the summit area. Furthermore, the pristine samples all reside in areas that rarely experience current magnitudes over 0.2 m/s, suggesting that above this the currents have the ability to erode ferromanganese crust. However, there is a strong overlap between the measured current magnitudes at the locations of partially and completely eroded crusts, as well as partial overlap with the current magnitudes measured at pristine crust locations. This complexity is likely due to the presence of cliffs and plateaus increasing current magnitudes and turbidity at a scale smaller than the model resolution.

Rare earth elements and yttrium (REY) variability with water depth in hydrogenetic ferromanganese crusts

The origins of ferromanganese (Fe–Mn) crusts that form in seawater and elemental partitioning into these crusts have previously been studied using samples from water depths shallower than 4 km. Here we report geochemical analyses of Fe–Mn crusts sampled from petit-spot volcanoes within the Pacific Ocean at water depths of 5.2–6.0 km. The Fe–Mn crusts have low Mn/Fe ratios (0.63–1.5), high contents of Co, Ni, and rare earth elements and Y (REY), and positive Ce anomalies, indicating a hydrogenetic origin. The Fe–Mn crusts are characterized by lower shale-normalized La/Pr ratios (LaSN/PrSN) than typical hydrogenetic Fe–Mn crusts from the Pacific Ocean. Despite negative LaSN/PrSN and NdSN/SmSN and positive EuSN/GdSN and DySN/HoSN correlations with water depth, the distribution coefficients of the REY are constant. This indicates that the observed REY variability with water depth in these hydrogenetic Fe–Mn crusts reflects that of seawater. In particular, a strong correlation between LaSN/PrSN and water depth has potential for use as a (paleo)ocean hydro-barometer. The variety of REY compositions of Fe–Mn crusts should be interpreted on the basis of distribution coefficients calculated for each water depth.

Metal flux as an alternative parameter in evaluating the resource potential for co-rich ferromanganese crusts

ABSTRACTWe propose a geochemical parameter, “metal flux” in evaluating hydrogenetic Co-rich ferromanganese crust deposits in the Pacific seamount area, that is based on physical, chemical, and geological characterization of the integrated growth piles of crusts. We calculated the metal flux for fifteen sites from different depths ranging between 900-6000m from different seamounts. The secular and areal variations of metal flux indicate a strong geological controls, and also can be a reliable tool for estimating an economic potential of the crusts. The Co flux decreases with increasing water depth, followed by almost constant flux of Ni and Mn. The Al and Fe fluxes vary with regions, indicating higher values in the western regions near the island arc probably related to a supply from the Asian continents. The results imply that Co, a redox sensitive metal element, is controlled by redox conditions of seawater, while Fe and Al are by terrigenous input. The metal flux reflects global and regional conditions and controls the compositional diversity of metals, thus consequently, the parameter can be a reliable powerful tool to estimate or single out more potential areas.

Magnetic stratigraphic dating of marine hydrogenetic ferromanganese crusts

Deep-sea hydrogenetic ferromanganese crusts are both potential polymetallic resources and records of long-term environmental changes. For palaeoceanographic studies, it is important to construct a detailed and reliable chronological framework. Here, we report the results of a detailed magnetostratigraphic and rock magnetic study of four hydrogenetic Fe-Mn crusts from the Pacific Ocean (PO-01), South China Sea (SCS-01, SCS-02) and Indian Ocean (IO-01). Two groups of characteristic remanent magnetization directions were defined with nearly antipodal normal and reversed polarities for samples PO-01, SCS-01 and SCS-02, indicating a primary record of the Earth’s magnetic field. The magnetostratigraphic framework, established via correlation with the Geomagnetic Polarity Time Scale 2012, implies growth rates of 4.82 mm/Ma, 4.95 mm/Ma, 4.48 mm/Ma and 11.28 mm/Ma for samples PO-01, SCS-01, SCS-02 and IO-01, respectively. Rock magnetic measurements revealed that the Fe-Mn crust samples from the Pacific Ocean and Indian Ocean were dominated by low coercivity, non-interacting, single-domain (SD) magnetite particles, whereas the South China Sea samples were dominated by SD/pseudo-single-domain (PSD) particles. Multidomain (MD) magnetite may also be present in all samples.

Reconstructing the Evolution of the Submarine Monterey Canyon System From Os, Nd, and Pb Isotopes in Hydrogenetic Fe‐Mn Crusts

AbstractThe sources of terrestrial material delivered to the California margin over the past 7 Myr were assessed using 187Os/188Os, Nd, and Pb isotopes in hydrogenetic ferromanganese crusts from three seamounts along the central and southern California margin. From 6.8 to 4.5 (±0.5) Ma, all three isotope systems show more radiogenic values at Davidson Seamount, located near the base of the Monterey Canyon System, than in Fe‐Mn crusts from the more remote Taney and Hoss Seamounts. At the Taney Seamounts, approximately 225 km farther offshore from Davidson Seamount, 187Os/188Os values, but not Pb and Nd isotope ratios, also deviate from the Cenozoic seawater curve toward more radiogenic values from 6.8 to 4.5 (±0.5) Ma. However, none of the isotope systems in Fe‐Mn crusts deviate from seawater at Hoss Seamount located approximately 450 km to the south. The regional gradients in isotope ratios indicate that substantial input of dissolved and particulate terrestrial material into the Monterey Canyon System is responsible for the local deviations in the seawater Nd, Pb, and Os isotope compositions from 6.8 to 4.5 (±0.5) Ma. The isotope ratios recorded in Fe‐Mn crusts are consistent with a southern Sierra Nevada or western Basin and Range provenance of the terrestrial material which was delivered by rivers to the canyon. The exhumation of the modern Monterey Canyon must have begun between 10 and 6.8 ± 0.5 Ma, as indicated by our data, the age of incised strata, and paleo‐location of the Monterey Canyon relative to the paleo‐coastline.

Microbial activity promotes the enrichment of cobalt over nickel on hydrogenetic ferromanganese crusts

ABSTRACTThe different mineral phases of the ferromanganese (Fe–Mn) crusts stem from the interaction of biotic and abiotic components. It is therefore vital to study the activity of these components to decipher their contribution to the enrichment/depletion of metals in the crust. Thus, the present study examined sorption and release of Co and Ni by Fe-Mn crusts with associated microbial communities in the presence and absence of the metabolic poison sodium azide (15 mM). The study was conducted in the presence (G+) and absence (G−) of added glucose (0.1%) at temperatures of 4 ± 1°C and 28 ± 2°C. Results showed that the microbial community had maximal sorption of Co of 66.12 µg g−1 at 4 ± 1°C in the absence of added glucose and 479.75 µg g−1 at 28 ± 2°C in the presence of added glucose. Maximum sorption of Ni in the absence of added glucose was 1.89 µg g−1 at 4 ± 1°C and release of Ni was 51.28 µg g−1 in the presence of added glucose. Under abiotic conditions with 15 mM sodium azide as a metabolic inhibitor, significant amounts of Co and Ni were released in the G+ medium. Total cell counts on the Fe-Mn crust in the presence of added glucose increased by an order of magnitude from 106 to 107 cells g−1 and in the absence of added glucose remained within the order of 106 cells g−1 irrespective of temperature of incubation. Microscopic observation of the samples from biotic incubations showed numerous bacterial cells, exopolysaccharides, and structures resembling secondary minerals formed by bacteria. The results indicate that bacteria promote the enrichment of Co and Ni on the hydrogenetic Fe-Mn crusts by sorption processes and release of Ni by reductive dissolution of the oxides. The higher enrichment of Co than Ni is attributed to the way in which microbes interact with the metals.

Bacterial activity in hydrogenetic ferromanganese crust from the Indian Ocean: a combined geochemical, experimental and pyrosequencing study

The Afanasiy-Nikitin Seamount (ANS) in the Equatorial Indian Ocean harbors hydrogenetic ferromanganese (Fe–Mn) crusts. It was hypothesized that the bacteria associated with the crust catalyze the precipitation of metal hydroxides in seawater more than abiotic dissolution, contributing to hydrogenetic accretion on the seamount. To test this hypothesis, Fe–Mn crust samples were collected from the flanks of the ANS. Geochemical properties of water samples collected were analyzed, and simulatory laboratory experiments were conducted to quantify bacterial accretion rates. Pyrosequencing was used to delineate the community associated with the crust. The environmental parameters of the water column indicated significant differences (p Mn (0.63) > Ni (0.003) > Co (0.002 mg g−1) with added glucose (0.01%) and Fe (9.09) > Mn (0.87) > Ni (0.0043) > Co (0.0008 mg g−1) without added glucose. Unlike the hydrothermal vent sites of the Pacific where e- and ζ-Proteobacteria were reported to be dominant, the hydrogenetic Fe–Mn crusts of the ANS revealed sequences related to known Fe-, Mn- and S-oxidizing bacteria of the γ- and α-Proteobacterial groups. Thus, the different selective pressures in the two environments could be one of the factors that have brought about a difference in their bacterial diversity. Besides, the ambient nutrient levels could have triggered the participation of the Proteobacterial community of the ANS in the precipitation of Fe–Mn rich minerals.