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James R. Hein

Publications and source records attributed to James R. Hein.

At least 19 recordsLinked to original sources

Hydrothermal manganese-oxide mineralization of a carbonate ooze, Samoan hotspot region, South Pacific Ocean

Low-temperature hydrothermal manganese oxides occur throughout the global oceans. However, the hydrothermal replacement of a carbonate ooze by manganese oxides is described here for the first time. The 24 samples dredged from three locations around the Territory of American Samoa in the South Pacific Ocean include six samples with remnant carbonate and volcaniclastic sediments, which we refer to as “low Mn,” and 18 samples in which the mineralization is pervasive and has replaced most original sediment, termed “high Mn.” The 18 high-Mn samples exhibit a mean Mn content of 51 wt.%. Higher Li and Mn contents and lower Fe contents in the high-Mn samples indicate a hydrothermal origin and distinguish these samples from hydrogenetic ferromanganese crusts. Mn-oxide layers are up to 90 mm thick, some with columns to 44 mm long and 10 mm wide, the magnitude of which has not been described previously. Samples are composed of birnessite and 10 Å phyllomanganate minerals. Textures of the thickest Mn layers indicate mineralization below the seabed from ascending fluids during multiple hydrothermal pulses. Mineralization took place by complete to partial replacement and cementation of foraminiferal sediments intermixed with volcaniclastic sediments in varying amounts. Our results highlight the production of carbonate sediment-hosted hydrothermal Mn oxides from multiple hydrothermal sources within the Samoan volcanic chain. The potential extensive distribution on the regional scale of this newly described mineralization process and unique element enrichments raise questions about its broader distribution globally and potential importance to hydrothermal processes, element mass balance, and seabed mineral resources.

Geochemistry, Geophysics, Geosystems↗

Neogene hydrothermal Fe- and Mn-oxide mineralization of Paleozoic continental rocks, Amerasia Basin, Arctic Ocean

Rocks dredged from water depths of 1,605, 2,500, 3,300, and 3,400 m in the Arctic Ocean included Paleozoic continental rocks pervasively mineralized during the Neogene by hydrothermal Fe and Mn oxides. Samples were recovered in three dredge hauls from the Chukchi Borderland and one from Mendeleev Ridge north of Alaska and eastern Siberia, respectively. Many of the rocks were so pervasively altered that the protolith could not be identified, while others had volcanic, plutonic, and metamorphic protoliths. The mineralized rocks were cemented and partly to wholly replaced by the hydrothermal oxides. The Amerasia Basin, where the Chukchi Borderland and Mendeleev Ridge occur, supports a series of faults and fractures that serve as major zones of crustal weakness. We propose that the stratabound hydrothermal deposits formed through the flux of hydrothermal fluids along Paleozoic and Mesozoic faults related to block faulting along a rifted margin during minor episodes of Neogene tectonism and were later exposed at the seafloor through slumping or other gravity processes. Tectonically driven hydrothermal circulation most likely facilitated the pervasive mineralization along fault surfaces via frictional heating, hydrofracturing brecciation, and low- to moderate temperature Fe- and Mn-rich hydrothermal fluids, which mineralized the crushed, altered, and brecciated rocks.

Geochemistry, Geophysics, Geosystems↗

Crystal chemistry of thallium in marine ferromanganese deposits

Our understanding of the up to 7 orders of magnitude partitioning of thallium (Tl) between seawater and ferromanganese (FeMn) deposits rests upon two foundations: (1) being able to quantify the Tl(I)/Tl(III) ratio that reflects the extent of the oxidative scavenging of Tl by vernadite (δ-MnO 2 ), the principle manganate mineral in oxic and suboxic environments, and (2) being able to determine the sorption sites and bonding environments of the Tl(I) and Tl(III) complexes on vernadite. We investigated these foundations by determining the oxidation state and chemical form of Tl in FeMn crusts and nodules from the global oceans at a Tl concentration ranging from several hundred ppm (mg/kg) down to the low ppm level. Seventeen hydrogenetic crusts and eleven nodules from the Pacific, Atlantic, Arctic, and Indian Oceans and Baltic Sea were characterized by chemical analysis, X-ray diffraction, Raman spectroscopy, Mn K-edge X-ray absorption near-edge structure (XANES) spectroscopy, Tl L 3 -edge high energy-resolution XANES (HR-XANES) spectroscopy, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The Tl concentration increases linearly from 1.5 to 319 ppm with the Mn/Fe ratio in Fe-vernadite from hydrogenetic crusts, whereas the percentage of Tl(III) to total Tl varies between 62 and 100% independent of both the Mn/Fe and Mn(III)/Mn(IV) ratios. The data, complemented by molecular modeling of the Tl(III) coordination and by XANES calculations, suggest that the enrichment of Tl in Fe-vernadite is driven by (1) the oxidative uptake of octahedrally coordinated Tl(III) above the vacant Mn(IV) sites and on the layer edges of the vernadite layers, and (2) the sorption of Tl(I) on the crystallographic site of Ba at the surface of the vernadite layers, which is an analogue to the surface site of K. Thus, Tl has a high affinity for vernadite regardless of its oxidation state, and the lack of correlation between Tl(III) and the Mn/Fe ratio in FeMn crusts is explained by the affinity of Tl(I) for the Ba site. The Tl concentration varies between 2 and 112 ppm in surface and buried nodules independent of the Mn/Fe ratio, and the percentage of Tl(III) varies between 0 and 100%. Nodules subjected to sediment diagenesis with replacement of layered vernadite by tunneled todorokite are depleted in Tl and have more reduced thallium. Knowledge of the complex interplay of mineralogy, surface chemical processes, and crystallographic siting is required to understand the variability of Tl concentrations, redox state, and acquisition processes by marine FeMn deposits.

ACS Earth and Space Chemistry↗

Estimates of metals contained in abyssal manganese nodules and ferromanganese crusts in the global ocean based on regional variations and genetic types of nodules

Deep-ocean ferromanganese crusts and manganese nodules are important marine repositories for global metals. Interest in these minerals as potential resources has led to detailed sampling in many regions of the global ocean, allowing for updated estimates of their global extent. Here, we present global estimates of total tonnage as well as contained metal concentrations and tonnages for ferromanganese crusts and manganese nodules using the most extensive compilation of geochemical data collected to date, along with updated boundaries of regions of interest for these minerals. We present results from mean composition calculated in two ways: first, a global flat average of regional mean compositions, and second, a regionally weighted average that considers differences in chemistry among genetic types and/or oceanographic and geologic settings for these mineral occurrences. For nodules, we use the three genetic types: (1) hydrogenetic, typified by nodules from the West Pacific Nodule Field and Penrhyn Basin; (2) diagenetic, typified by nodules from the Peru Basin; (3) mixed hydrogenetic-diagenetic, typified by nodules from the Clarion–Clipperton Zone and the Central Indian Ocean Basin, and Atlantic Ocean regional type hydrogenetic nodules. All crusts considered here are of hydrogenetic origin, which we divide into seven regional types that reflect a combination of ocean basin and other source inputs. Crust types include Arctic Ocean, Atlantic Ocean, Indian Ocean, Continental Margin, Prime Crust Zone (PCZ), North Pacific (non PCZ), and South Pacific. Based on our areal estimates, we find that abyssal regions likely to contain hydrogenetic-type nodules are by far the most widespread in the global ocean (47% of total area), Atlantic Ocean (28%) are next, followed by mixed diagenetic-hydrogenetic (22%) and diagenetic (3%) types. For crusts, the Prime Crust Zone is the most extensive global region (27% of total area) followed by South Pacific (20%), Indian Ocean (18%), North Pacific (12%), Continental Margins (11%), Atlantic Ocean (10%), and Arctic Ocean (2%) types. The global total tonnage estimates that we calculated from this method are 21 × 10 10 dry tons for manganese nodules, within the range of previous estimates, and 93 × 10 10 dry tons for ferromanganese crusts, which is 4.5 times higher than the 20 × 10 10 dry tons reported by Hein et al. (2003). This geology and oceanography driven approach to marine mineral quantification contrasts with estimates typically carried out for terrestrial mineral resource deposits. Nevertheless, these estimates and the data that support them demonstrate that marine minerals are an impressive repository for global metals.

Book chapter↗

Geochemical insights into formation of enigmatic ironstones from Rio Grande rise, South Atlantic Ocean

Rio Grande Rise (RGR) is an intraplate oceanic elevation in the South Atlantic Ocean that formed at a hotspot on the Mid-Atlantic Ridge during the Cretaceous. In spreading center and hotspot environments, ironstones form mainly by biomineralization of reduced Fe from hydrothermal fluids or oxidation of sulfide deposits. However, RGR has been considered aseismic and volcanically inactive for the past 46 Ma. Here, we investigate the origin of ironstones collected from the summit of RGR using multiple techniques: petrographic observations, X-ray diffraction, U-Th/He geochronology, and chemical composition. The ironstones from RGR consist of finely laminated goethite containing igneous rock fragments, carbonate fluorapatite, and calcite. Our results suggest that Fe oxyhydroxides were precipitated by Fe-oxidizing bacteria forming bacterial mats. The bacterial Fe mats underwent compaction, dewatering, goethite crystallization, and cementation that created the ironstone deposits. U-Th/He geochronology reveals protracted goethite minimum ages extending from the late Miocene to the Quaternary, probably due to multiple generations of mats, slow mineralization rates, and Fe-oxide dissolution-reprecipitation cycles. Flame-like goethite structures underneath FeMn crusts and a chimney-shaped goethite sample with a central channel indicate that the dewatering fluid flowed upward through the deposits, or a thermal fluid source may have been introduced from below the ironstone deposits. High Fe/Mn ratios, low trace metals contents (Ni + Co + Cu), and very low Fe/REY ratios suggest ironstone precipitation from a hydrothermal fluid; however, REY SN plots and bivariate Ce SN /Ce SN ⁎ versus Y SN /Ho SN and Ce SN /Ce SN ⁎ versus Nd plots are inconclusive, and a proximal source of magma was unlikely during the period of mat formation. Given this evidence, we hypothesize that a geothermal circulation system may have facilitated ironstone mineralization at RGR.

Marine Geology↗

Deep-ocean polymetallic nodules and cobalt-rich ferromanganese crusts in the global ocean: New sources for critical metals

The transition from a global hydrocarbon economy to a green energy economy and the rapidly growing middle class in developing countries are driving the need for considerable new sources of critical materials. Deep-ocean minerals, namely cobalt-rich ferromanganese crusts and polymetallic nodules, are two such new resources generating interest. Polymetallic nodules are essentially two-dimensional mineral deposits sitting on abyssal plain sediments at about 3,500–6,000 m water depths. Metals of economic interest enriched in nodules include nickel, copper, manganese, cobalt and molybdenum. Cobalt-rich ferromanganese crusts are also two-dimensional deposits forming pavements on rock outcrops on seamounts and ridges at water depths of 400–7,000 m. Metals of economic interest for crusts include cobalt, manganese, nickel, molybdenum, tellurium, platinum, vanadium and rare earth elements. A conservative estimate is that 21.1 billion dry tons of polymetallic nodules exist in the Clarion-Clipperton Zone ( CCZ ) manganese nodule field, the largest in area and tonnage of the known global nodule fields. Based on that estimate, tonnages of many critical metals in the CCZ nodules are greater than those found in global terrestrial reserves. About 7.5 billion dry tons of cobalt-rich ferromanganese crusts are estimated to occur in the Pacific Ocean Prime Crust Zone, the area with the highest tonnage of critical-metal-rich crust deposits, with many elements contained therein estimated to be greater than those found in global terrestrial reserves. Deep-ocean mining has not yet been carried out in the Exclusive Economic Zone of any nation, nor in the Areas beyond national jurisdiction, although extensive mineral exploration and environmental studies are being conducted and exploitation regulations codified, indicating that mining activities will likely begin in the near future. If deep-ocean mining follows the evolution of offshore production of petroleum, we can expect that about 35–45 per cent of the demand for critical metals will come from deep-ocean mines by 2065.

Book chapter↗

Miocene phosphatization of rocks from the summit of Rio Grande Rise, Southwest Atlantic Ocean

Marine phosphorites are an important part of the oceanic phosphorus cycle and are related to the effects of long-term global climate changes. We use petrography, mineralogy, rare earth elements contents, and 87 Sr/ 86 Sr-determined carbonate fluorapatite (CFA) and calcite ages to investigate the paragenesis and history of phosphatization of carbonate sediments, limestones, ferromanganese crusts, and ironstones from the summit of Rio Grande Rise (RGR), Southwest Atlantic Ocean. Phosphatization of all the rock types occurred throughout the Miocene from 20.2 to 6.8 million years ago (Ma), and occasionally during the Quaternary, mainly through the cementation of carbonate sediments by cryptocrystalline CFA, likely involving the dissolution of the smaller size fraction of foraminifera-nannofossil ooze. Porosity/permeability and abundance of fine calcite material were important factors determining the intensity of phosphatization of the various rock types. Phosphatization was initiated during a transition to a more dynamic circulation system in the South Atlantic Ocean, which remobilized phosphorus from deeper waters and increased primary productivity that culminated with the middle-Miocene Climatic Optimum between ∼17 and 14.8 Ma. The relatively shallow-water depth of RGR summit during the Miocene provided proximity to the oxygen minimum zone, a reservoir for reactive phosphorus, especially during periods of enhanced phosphorus cycling spurred by surface primary productivity. The cessation of phosphatization at RGR resulted from a rapidly cooling and dry climate that characterized the Miocene-Pliocene transition. Our results support previous observations that periods of broadly intensified ocean circulation and local hydrodynamic changes were the key paleoceanographic links to phosphorite formation.

Paleoceanography and Paleoclimatology↗

Ocean floor manganese deposits

Much of the dissolved Mn delivered to the oceans is slowly oxidized and precipitated alongside varying amounts of Fe into Mn and ferromanganese (FeMn) mineral deposits that occur extensively in the deep ocean wherever sediment accumulation is low and substrate is available. FeMn crusts grow as pavements on rock outcrops throughout the global ocean whereas nodules form as individual FeMn-encrusted particles on the sediment-covered abyssal plains. Both crusts and nodules are composed predominantly of Fe and Mn oxide minerals that precipitate from seawater and for some nodules also from porewaters of deep-sea sediment. In contrast, hydrothermal oxide deposits consist predominantly of Mn or Fe oxide. FeMn crusts and nodules exhibit very high specific surface areas that allow them to scavenge abundant metals and other elements, recording the history of the source waters. Crusts especially serve as an important record of paleoceanographic conditions over the past 70 + million years. Critical metals essential to many computer, military, and green technologies are enriched in crust and nodule deposits to concentrations high enough to compare with, or exceed, typical terrestrial deposits, and they can be considered as potential resources for mining in the near future. Twenty-three contracts pertaining to exploration for nodules and crusts have been signed with the International Seabed Authority, and resource/reserve, baseline, and environmental impact assessments are underway. Many challenges remain to be addressed before full-scale mining of marine FeMn deposits will occur. However, their unique genesis and the growing worldwide need for rare and critical metals keep these deep-ocean deposits relevant to industry, scientists, and governments.

Book chapter↗

Changes in seabed mining

Chapter 23 of the First World Ocean Assessment (WOA I) focused on marine mining, and particularly on established extractive industries, which are predominantly confined to near-shore areas, where shallow-water, near-shore aggregate and placer deposits, and somewhat deeper water phosphate deposits are found (United Nations, 2017a). At the time of publication, there were no commercially developed deep-water seabed mining (DSM) deposits but an assessment of mining leases and exploration activity was included. Since WOA I, the number of deep-water (depths greater than 200 m below the ocean surface) seabed exploration licenses has increased both within national jurisdictions of coastal, island and archipelagic States, and beyond in the Area (the seabed, ocean floor and subsoil thereof beyond the limits of national jurisdiction) under the administration of the International Seabed Authority (ISA). For the first time, in 2017 deep-water seabed test-mining was carried out by Japan at a water depth of 1,600 m within its exclusive economic zone (EEZ) (METI, 2017). The update in the present Chapter will focus on the nascent deep-water seabed mining industry and mineral deposits. Hereafter, we use seabed for deep-water seabed. Environmental issues focused on impacts from dredging activities and a list of references for some mining operations were provided. However, WOA I could not provide an environmental baseline for DSM and considered that environmental, social and economic aspects were often not adequately understood with available data. Data on potential environmental impacts are still scarce and can differ greatly between mineral extraction from near-shore and seabed mining sites. Information on economic benefits, and to some extent social impacts, of mining is becoming progressively more accessible due to several initiatives promoting an increase in transparency of extractive industries. In 2015, the 2030 Agenda for Sustainable Development was adopted by all United Nations Member States. It includes 17 Sustainable Development Goals (SDGs) to be addressed on the basis of a global partnership. DSM activities may have implications for the achievement of SDGs 1, 5, 7–10, 12–14, and 17.

Book chapter↗

Sphalerite oxidation in seawater with covellite: Implications for seafloor massive sulfide deposits and mine waste

Metal sulfide minerals exist in several marine environments and are in thermodynamic disequilibrium with oxygenated seawater from the time of their formation. Oxidation is both ubiquitous and heterogeneous, as observational and experimental evidence demonstrates that sulfide minerals may oxidize completely on decadal timescales (hydrothermal plumes) or incompletely in billions of years (mineral deposits); however, the processes, rates, and interactions among minerals as oxidative dissolution occurs are not well understood. Added impetus to understanding these processes exists due to the potential for mining of seafloor massive sulfide deposits and potential environmental impacts of that activity. Here, we present a laboratory-based experimental study on the galvanic oxidation of sphalerite and synthesized zinc sulfide and coupled to covellite. We find that, in contrast to single-mineral reactions, coupled mineral reactions are at least 2 orders of magnitude more rapid, light independent, and have a lower apparent activation energy for oxidation. These results begin to provide insight into observed differences between laboratory and environmentally observed oxidation rates and are a step in the direction of more accurately predicting environmental rates as well as any changes to those rates from anthropogenic disturbances.

ACS Earth and Space Chemistry↗

The effects of phosphatization on the mineral associations and speciation of Pb in ferromanganese crusts

The older layers of thick ferromanganese (FeMn) crusts from the central Pacific Ocean have undergone diagenetic phosphatization, during which carbonate fluorapatite (CFA) filled fractures and pore space and replaced carbonates. The effects of phosphatization on individual trace metal concentrations, speciation, and phase associations in FeMn crusts remain poorly understood yet may be important to metal enrichment mechanisms, paleoceanography, and extractive metallurgy. This study examines the concentrations, speciation, and mineral phase associations of Pb in phosphatized and nonphosphatized layers within three Pacific Ocean crusts using standard chemical and mineralogical techniques, in addition to bulk X-ray absorption spectroscopy (XAS) and microfocused X-ray fluorescence (μ-XRF) mapping. Our findings challenge the conclusions of previous works, which reported that most Pb in phosphatized crusts was associated with the CFA-dominated residual phase after sequential leaching experiments. These results were interpreted as an indication of Pb transfer from the oxide phases to diagenetic CFA during phosphatization. However, our results reveal an inverse correlation of Pb with Ca and P in the μ-XRF mapping of in situ FeMn crust sections and bulk chemistry. Furthermore, XAS measurements reveal that Pb speciation in bulk phosphatized FeMn crust layers is very similar to nonphosphatized layers, indicating only minor, if any, change in speciation during diagenetic phosphatization. Small differences in the EXAFS spectra for one highly phosphatized layer indicate that minor amounts of Pb may have been altered during phosphatization, but the new Pb-bearing phase was not unequivocally identified. Taken together, our results demonstrate that Pb speciation is not significantly affected by phosphatization.

Earth and Space Chemistry↗

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, 87 Sr/ 86 Sr 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.

Rio Grande Rise↗

Geographic and oceanographic influences on ferromanganese crust composition along a Pacific Ocean meridional transect, 14N to 14S

The 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.

Geochemistry, Geophysics, Geosystems↗

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.

Marine Geology↗

Mineralization at oceanic transform faults and fracture zones

Mineral formation in the modern oceans can take place over millions of years as a result precipitation from ambient ocean water, or orders of magnitude more rapidly from hydrothermal activity related to magmatic and tectonic processes. Here, we review associations between transform faults and related fracture zones and marine minerals. We define marine transform faults as strike-slip or oblique faults that accommodate lateral offsets along plate boundaries or shifting crustal blocks, and fracture zones as relicts of transform faulting extending beyond mid-ocean ridge offsets. We consider specifically the modern ocean and exclude regions where the transform or fracture has clearly not generated the mineral deposit, such as the Clarion-Clipperton fracture zone manganese nodule field. As a result, the summarized deposits are mainly hydrothermal in origin. Oceanic transform faulting has rarely been considered of interest for the mineralization and formation of ore deposits; however, there are locations in the modern oceans where transform faults and fracture zones are spatially related to mineral deposits. These occurrences suggest that transform faulting and fracture zones may be linked to mineralization at (A) intersections with other tectonic features, (B) where transform faults begin to resemble rifts through intra-transform crustal thinning, spreading, and the formation of pull-apart basins, and (C) as a result of serpentinization reactions due to exposure of deep-seated rocks by fracturing and faulting.

Book chapter↗

Formation and occurrence of ferromanganese crusts: Earth’s storehouse for critical metals

Marine ferromanganese oxide crusts (Fe–Mn crusts) are potentially important metal resources formed on the seafloor by precipitation of dissolved and colloidal components from ambient seawater onto rocky surfaces. The unique properties and slow growth rates of the crusts promote adsorption of numerous elements from seawater: some, such as Te and Co, reach concentrations rarely encountered elsewhere in nature. Consequently, Fe–Mn crusts are potential sources of metals used in technologies considered essential for the transition to a low-carbon economy. However, the precise distributions and metal concentrations at regional and local scales are poorly constrained because of the diversity of geological, oceanographic and chemical processes involved in their formation.

Elements↗

Mineral phase-element associations based on sequential leaching of ferromanganese crusts, Amerasia Basin Arctic Ocean

Ferromanganese (FeMn) crusts from Mendeleev Ridge, Chukchi Borderland, and Alpha Ridge, in the Amerasia Basin, Arctic Ocean, are similar based on morphology and chemical composition. The crusts are characterized by a two- to four-layered stratigraphy. The chemical composition of the Arctic crusts differs significantly from hydrogenetic crusts from elsewhere of global ocean by high mean Fe/Mn ratios, high As, Li, V, Sc, and Th concentrations, and high detrital contents. Here, we present element distributions through crust stratigraphic sections and element phase association using several complementary techniques such as SEM-EDS, LA-ICP-MS, and sequential leaching, a widely employed method of element phase association that dissolves mineral phases of different stability step-by-step: Exchangeable cations and Ca carbonates, Mn-oxides, Fe-hydroxides, and residual fraction. Sequential leaching shows that the Arctic crusts have higher contents of most elements characteristic of the aluminosilicate phase than do Pacific crusts. Elements have similar distributions between the hydrogenetic Mn and Fe phases in all the Arctic and Pacific crusts. The main host phases for the elements enriched in the Arctic crusts over Pacific crusts (Li, As, Th, and V) are the Mn-phase for Li and Fe-phase for As, Th, and V; those elements also have higher contents in the residual aluminosilicate phase. Thus, higher concentrations of Li, As, Th, and V likely occur in the dissolved and particulate phases in bottom waters where the Arctic crusts grow, which has been shown to be true for Sc, also highly enriched in the crusts. The phase distributions of elements within the crust layers is mostly consistent among the Arctic crusts, being somewhat different in element concentrations in the residual phase.

Minerals↗

Reconstructing the evolution of the submarine Monterey Canyon System from Os, Nd, and Pb isotopes in hydrogenetic Fe-Mn crusts

The sources of terrestrial material delivered to the California margin over the past 7 Myr were assessed using 187 Os/ 188 Os, 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, 187 Os/ 188 Os values, but not Pb and Nd isotope ratios, also deviate from the Cenozoic seawater curve towards 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.

California↗