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Kira Mizell

Publications and source records attributed to Kira Mizell.

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↗

Extremophile hotspots linked to containerized industrial waste dumping in a deep-sea basin

Decaying barrels on the seafloor linked to DDT contamination have raised concerns about the public health implications of decades old industrial waste dumped off the coast of Los Angeles. To explore their contents, we collected sediment cores perpendicular to five deep-sea barrels. The concentration of DDT and its breakdown products were highly elevated relative to control sites yet did not vary with distance from the barrels, suggesting that they were not associated with the contamination. Sediment cores collected through white halos surrounding three barrels were enriched in calcite and had elevated pH. The associated microbial communities were low diversity and dominated by alkalophilic bacteria with metagenome-assembled genomes adapted to high pH. A solid concretion sampled between a white halo and barrel was composed of brucite, a magnesium hydroxide mineral that forms at high pH. Based on these findings, we postulate that leakage of containerized alkaline waste triggered the formation of mineral concretions that are slowly dissolving and raising the pH of the surrounding sediment pore water. This selects for taxa adapted to extreme alkalinity and drives the precipitation of “anthropogenic” carbonates forming white halos, which serve as a visual identifier of barrels that contained alkaline waste. Remarkably, containerized alkaline waste discarded >50 years ago represents a persistent pollutant creating localized mineral formations and microbial communities that resemble those observed at some hydrothermal systems. These formations were observed at one-third of the visually identified barrels in the San Pedro Basin and have unforeseen, long-term consequences for benthic communities in the region.

California↗

Megafaunal community structure on ferromanganese and phosphorite hardgrounds in the Southern California Borderland

The Southern California Borderland (SCB) is a topographically complex region on the active continental margin that hosts varied hardground habitats, including ferromanganese (FeMn) crusts and phosphorites, marine minerals being considered for resource extraction. The SCB is influenced by seasonal upwelling and terrestrial inputs, and has a well-defined oxygen-minimum zone (OMZ). We analyzed megafaunal community composition, density, and diversity across 41 ROV video transects at 10 SCB hard substrate sites spanning depth (378–2765 m), temperature (1.79–7.96 °C), and oxygen (3.91–105.67 μM) gradients, with varying rock types (FeMn crusts, phosphorites, other rocks). We counted 32,426 individuals representing 146 unique taxa over a total area of 21,935 m 2 . Echinodermata contributed 48 % of the total abundance; Cnidaria 24 %; Porifera 13 %; Annelida 6 %; Arthropoda 6 %; Chordata 2 %; Mollusca, Foraminifera, and Hemichordata <1 %. Megafauna communities showed clear heterogeneity, with density, diversity, and community composition varying among transects within sites and across sites. Rock type recorded no influence on megafaunal density, but habitats that included FeMn crusts had higher diversity and distinct taxonomic composition. Location, depth, and oxygen were the most important variables explaining variance among megafaunal communities, with distinct communities formed at deeper depths and within the OMZ. This study provides baseline information about the megafauna inhabiting SCB hardgrounds, particularly those associated with minerals considered for their resource potential. It extends existing documentation of such communities to greater depths, reveals increased representation of sponges and corals below 1000 m, and highlights the variability within and among deep-sea megafaunal communities, offering context for informed policy decisions.

Southern California borderland↗

The influence of nodule versus crust morphology on the composition of seamount-hosted ferromanganese minerals

Ferromanganese mineral precipitation in the global oceans is ubiquitous, occurring in the form of both crusts and nodules at a broad range of depths and seafloor terrains. Although ferromanganese crusts and nodules are both composed of ferromanganese minerals, mineralogy and mean element concentrations compiled for regional crust versus nodule occurrences differ. Notably, most published compilations compare nodules from abyssal plain sediments to crusts forming on seamounts, and do not address the question as to whether mineral morphology may affect the composition of crusts and nodules in addition to environmental factors. To address this, we have compiled a dataset of co-located hydrogenetic (seawater sourced) open-ocean ferromanganese crusts and seamount-hosted nodules. The preliminary data presented here support our hypothesis that co-located crusts and nodules exhibit similar compositions, both in terms of their mineralogy and mean element concentrations, as well as overall variance in concentrations for any given element. These data indicate that local processes influence sample-to-sample variation in both crusts and nodules, in contrast to broader ferromanganese variation reported between open-ocean seamounts- hosted crusts and abyssal plain-hosted nodules.

Conference Paper↗

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↗

Deep-ocean macrofaunal assemblages on ferromanganese and phosphorite-rich substrates in the Southern California Borderland

Mineral-rich hardgrounds, such as ferromanganese (FeMn) crusts and phosphorites, occur on seamounts and continental margins, gaining attention for their resource potential due to their enrichment in valuable metals in some regions. This study focuses on the Southern California Borderland (SCB), an area characterized by uneven and heterogeneous topography featuring FeMn crusts, phosphorites, basalt, and sedimentary rocks that occur at varying depths and are exposed to a range of oxygen concentrations. Due to its heterogeneity, this region serves as an optimal setting for investigating the relationship between mineral-rich hardgrounds and benthic fauna. This study characterizes the density, diversity, and community composition of macrofauna (>300 μm) on hardgrounds as a function of substrate type and environment (depth and oxygen ranges). Rocks and their macrofauna were sampled quantitatively using remotely operated vehicles (ROVs) during expeditions in 2020 and 2021 at depths above, within, and below the oxygen minimum zone (OMZ). A total of 3,555 macrofauna individuals were counted and 416 different morphospecies (excluding encrusting bryozoans and hydrozoans) were identified from 82 rocks at depths between 231 and 2,688 m. Average density for SCB macrofauna was 11.08 ± 0.87 ind. 200 cm −2 and mean Shannon-Wiener diversity per rock (H′ [loge] ) was 2.22 ± 0.07. A relationship was found between substrate type and macrofaunal communities. Phosphorite rocks had the highest H′ of the four substrates compared on a per-rock basis. However, when samples were pooled by substrate, FeMn crusts had the highest H′ and rarefaction diversity. Of all the environmental variables examined, water depth explained the largest variance in macrofaunal community composition. Macrofaunal density and diversity values were similar at sites within and outside the OMZ. This study is the first to analyze the macrofaunal communities of mineral-rich hardgrounds in the SCB, which support deep-ocean biodiversity by acting as specialized substrates for macrofaunal communities. Understanding the intricate relationships between macrofaunal assemblages and mineral-rich substrates may inform effects from environmental disruptions associated with deep-seabed mining or climate change. The findings contribute baseline information useful for effective conservation and management of the SCB and will support scientists in monitoring changes in these communities due to environmental disturbance or human impact in the future.

California↗

Invertebrate trophic structure on marine ferromanganese and phosphorite hardgrounds

The Southern California Borderland hosts a variety of geologic and oceanographic features that allow for diverse habitats to occur in a restricted region with a strong oxygen minimum zone (OMZ) and hard substrates. These include ferromanganese (FeMn) crusts and phosphorites targeted for deep-seabed mining in other regions. Baseline studies regarding hardground macro- (> 0.3 mm) and megafaunal (> 2 cm) invertebrates are lacking, although they contribute to understanding nutrient cycling and resilience of deep-sea communities to ocean deoxygenation, fishing, or mineral extraction. With the goal of understanding how substrate type, depth, and dissolved oxygen concentration influence invertebrate trophic structure, we surveyed δ 13 C and δ 15 N values of invertebrates on hard substrates on the Southern California Borderland margin along a depth gradient (120–2400 m) through the OMZ at inshore (< 100 km from shore) and offshore (100–250 km from shore) sites, using generalized additive models and community-level metrics. Macrofaunal isotopic values correlate with substrate type, exhibiting higher trophic diversity on FeMn crusts and specialized communities on phosphorites. Megafaunal isotopic values correlate with proximity to shore; animals offshore seem to depend more on phytoplanktonic production than animals inshore. In general, δ 15 N increased with decreasing dissolved oxygen and increasing depth, possibly due to remineralization processes within the OMZ and with depth. We discuss how feeding modes and community composition might influence the observed patterns. This study elucidates the importance of the environmental context in shaping invertebrate trophic structure on continental margins and provides baseline knowledge that may be useful in regions where these minerals are targeted for extraction.

Limnology and Oceanography↗

Metal release from manganese nodules in anoxic seawater and implications for deep-sea mining dewatering operations

The potential mining of deep-sea polymetallic nodules has been gaining increasing attention due to their enrichment in metals essential for a low-carbon future. To date, there have been few scientific studies concerning the geochemical consequences of dewatered mining waste discharge into the pelagic water column, which can inform best practices in future mining operations. Here, we report the results of laboratory incubation experiments that simulate mining discharge into anoxic waters such as those that overlie potential mining sites in the North Pacific Ocean. We find that manganese nodules are reductively dissolved, with an apparent activation energy of 42.8 kJ mol –1 , leading to the release of associated metals in the order manganese > nickel > copper > cobalt > cadmium > lead. The composition of trace metals released during the incubation allows us to estimate a likely trace metal budget from the simulated dewatering waste plume. These estimates suggest that released cobalt and copper are the most enriched trace metals within the plume, up to ∼15 times more elevated than the background seawater. High copper concentrations can be toxic to marine organisms. Future work on metal toxicity to mesopelagic communities could help us better understand the ecological effects of these fluxes of trace metals.

ACS ES&T Water↗

Marine minerals in Alaska — A review of coastal and deep-ocean regions

Minerals occurring in marine environments span the globe and encompass a broad range of mineral categories, forming within varied geologic and oceanographic settings. They occur in coastal regions, either from the continuation or mechanical reworking of terrestrial mineralization, as well as in the deep ocean, from diagenetic, hydrogenetic, and hydrothermal processes. The oceans cover most of the Earth’s surface and as a result, any inventory of global resources is incomplete without the inclusion of marine minerals. This study by the U.S. Geological Survey reviews current knowledge regarding deep-ocean and coastal marine minerals within the marine areas surrounding Alaska, including the Alaska Outer Continental Shelf (OCS). For the purposes of this study, we have divided these areas in to eight regions: (1) Gulf of Alaska seamounts, (2) Chukchi Borderland, (3) Canada Basin, (4) Aleutian Arc, (5) Seward Peninsula, (6) Goodnews Bay, (7) Bristol Bay and Alaska Peninsula, and (8) southern and southeastern Alaska. The Alaska OCS encompasses several areas broadly conducive to marine mineral formation, including extensional basins resulting from an active subduction zone where massive sulfide deposits may form, deep abyssal plains with conditions that may lead to manganese nodule formation, seamounts that can provide substrate for the growth of ferromanganese crusts, and erosional settings and submerged continental crust where placer deposits are found. For deep-ocean hydrothermal minerals and manganese nodules, the Alaska OCS contains prospective regions, including the Canada Basin and the Aleutian Arc; however, no such minerals have yet been identified. We explore the probability that these minerals occur based on reviews of existing geologic and oceanographic data within the relevant sections. In regions far from shore data are limited. Deep-ocean ferromanganese crusts are known to occur in two regions: (1) the Gulf of Alaska seamounts and (2) the Chukchi Borderland in the Arctic Ocean. Limited sampling has occurred in both regions, and along the Chukchi Borderland the sampling was outside of the OCS and the U.S. Exclusive Economic Zone. Data relevant to coastal minerals is more extensive, and in some places fairly systematic sampling was conducted. Several nearshore placer deposits have been exploited for decades; however, the potential for nearshore extension of terrestrial ore deposits is less well considered. This contribution considers the state of knowledge regarding marine mineral occurrences within the Alaska regions and identifies the data gaps in order to help inform future marine mineral related research efforts around Alaska.

Alaska↗

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↗

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↗