Marine phosphorites are known to concentrate rare earth elements and yttrium (REY) during early diagenetic formation. Much of the REY data available are decades old and incomplete, and there has not been a systematic study of REY distributions in marine phosphorite deposits that formed over a range of oceanic environments. Consequently, we initiated this study to determine if marine phosphorite deposits found in the global ocean host REY concentrations of high enough grade to be of economic interest. This paper addresses continental-margin (CM) and open-ocean seamount phosphorites. All 75 samples analyzed are composed predominantly of carbonate fluorapatite and minor detrital and authigenic minerals. CM phosphorites have low total REY contents (mean 161 ppm) and high heavy REY (HREY) complements (mean 49%), while seamount phosphorites have 4–6 times higher individual REY contents (except for Ce, which is subequal; mean ΣREY 727 ppm), and very high HREY complements (mean 60%). The predominant causes of higher concentrations and larger HREY complements in seamount phosphorites compared to CM phosphorites are age, changes in seawater REY concentrations over time, water depth of formation, changes in pH and complexing ligands, and differences in organic carbon content in the depositional environments. Potential ore deposits with high HREY complements, like the marine phosphorites analyzed here, could help supply the HREY needed for high-tech and green-tech applications without creating an oversupply of the LREY.

The Rio Grande Rise (RGR) is a large elevation in the Atlantic Ocean and known to host potential mineral resources of ferromanganese crusts (Fe–Mn), but no investigation into their general characteristics have been made in detail. Here, we investigate the chemical and mineralogical composition, growth rates and ages of initiation, and phosphatization of relatively shallow-water (650–825 m) Fe–Mn crusts dredged from the summit of RGR by using computed tomography, X-ray diffraction, ⁸⁷Sr/⁸⁶Sr ratios, U–Th isotopes, and various analytical techniques to determine their chemical composition. Fe–Mn crusts from RGR have two distinct generations. The older one has an estimated age of initiation around 48–55 Ma and was extensively affected by post-depositional processes under suboxic conditions resulting in phosphatization during the Miocene (from 20 to 6.8 Ma). As a result, the older generation shows characteristics of diagenetic Fe–Mn deposits, such as low Fe/Mn ratios (mean 0.52), high Mn, Ni, and Li contents and the presence of a 10 Å phyllomanganate, combined with the highest P content among crusts (up to 7.7 wt %). The younger generation is typical of hydrogenetic crusts formed under oxic conditions, with a mean Fe/Mn ratio of 0.75 and mean Co content of 0.66 wt %, and has the highest mean contents of Bi, Nb, Ni, Te, Rh, Ru, and Pt among crusts formed elsewhere. The regeneration of nutrients from local biological productivity in the water column is the main source of metals to crusts, providing mainly metals that regenerate rapidly in the water column and are made available at relatively shallow water depths (Ni, As, V, and Cd), at the expense of metals of slower regeneration (Si and Cu). Additionally, important contributions of nutrients may derive from various water masses, especially the South Atlantic Mode Water and Antarctic Intermediate Water (AAIW). Bulk Fe–Mn crusts from the summit of RGR plateau are generally depleted in metals considered of greatest economic interest in crusts like Co, REE, Mo, Te, and Zr, but are the most enriched in the critical metals Ni and Li compared to other crusts. Further investigations are warranted on Fe–Mn crusts from deeper-water depths along the RGR plateau and surrounding areas, which would less likely be affected by phosphatization.

Little is known about marine mineral deposits in the Arctic Ocean, an ocean dominated by continental shelf and basins semi‐closed to deep‐water circulation. Here, we present data for ferromanganese crusts and nodules collected from the Amerasia Arctic Ocean in 2008, 2009, and 2012 (HLY0805, HLY0905, and HLY1202). We determined mineral and chemical compositions of the crusts and nodules and the onset of their formation. Water column samples from the GEOTRACES program were analyzed for dissolved and particulate scandium concentrations, an element uniquely enriched in these deposits. The Arctic crusts and nodules are characterized by unique mineral and chemical compositions with atypically high growth rates, detrital contents, Fe/Mn ratios, and low Si/Al ratios, compared to deposits found elsewhere. High detritus reflects erosion of submarine outcrops and North America and Siberia cratons, transport by rivers and glaciers to the sea, and distribution by sea ice, brines, and currents. Uniquely high Fe/Mn ratios are attributed to expansive continental shelves, where diagenetic cycling releases Fe to bottom waters, and density flows transport shelf bottom water to the open Arctic Ocean. Low Mn contents reflect the lack of a mid‐water oxygen minimum zone that would act as a reservoir for dissolved Mn. The potential host phases and sources for elements with uniquely high contents are discussed with an emphasis on scandium. Scandium sorption onto Fe oxyhydroxides and Sc‐rich detritus account for atypically high scandium contents. The opening of Fram Strait in the Miocene and ventilation of the deep basins initiated Fe‐Mn crust growth ∼15 Myr ago.

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 ⁸⁷Sr/⁸⁶Sr‐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.

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.