Arctic deep water ferromanganese-oxide deposits reflect the unique characteristics of the Arctic Ocean

Author Posting. © American Geophysical Union, 2017. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry, Geophysics, Geosystems 18 (2017): 3771–3800, doi:10.1002/2017GC007186.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.National Science Foundation Grant Numbers: 1434493, 1713677; NSF-OCE Grant Number: 15358542018-05-0

Multidisciplinary scientific cruise to the Rio Grande Rise

The full text of this article can be freely accessed on the publisher's website

The Effects of Regional Oceanographic Conditions on the Geochemistry of Ferromanganese Crusts from the West-Central Pacific Ocean

Ferromanganese (FeMn) crusts are of interest and clear importance both as a unique paleoceanographic archive of seawater chemistry and as a potential resource for valuable and critical metals. Presently, there is a need to shift FeMn crust research from purely exploration-based studies to more targeted expeditions that can precisely locate FeMn crusts with characteristics of interest for scientific research and resource evaluation. Understanding the influence of general oceanographic conditions on FeMn crust formation is key to defining permissive regions. This thesis investigates variations in the geochemistry of FeMn crusts from the west-central Pacific that are associated with regional oceanographic conditions, including proximity to the oxygen minimum zone and high biological productivity maintained at the equator, as well as water depth controls and the effects of diagenetic phosphatization. Chemical analysis of over 60 FeMn crusts reveals that the oxygen minimum zones in the northern and southern tropics in the west Pacific exhibit strong controls on the composition of recent FeMn crust growth as well bulk FeMn crusts. Manganese contents are increased near the oxygen minimum zones, which is shown quantitatively for a broad region in this thesis for the first time. Iron is instead enriched in deeper waters where oxidation of iron is increased, which may be caused by higher carbonate ion concentrations and pH at depth and the availability of deep sources of iron. High biological productivity in the equatorial upwelling zone enriches iron, magnesium, and barium in FeMn crusts that are forming below this zone due to increased efficiency of the biological pump. Diagenetic phosphatization is commonly observed in crusts from depths above 2000 meters, but does not exceedingly dilute manganese oxides or elements of economic interest. Synchrotron analyses of phosphatized FeMn crust layers indicate that phosphatization does not change the speciation of lead as hypothesized based on previous sequential leaching studies. Overall, is it shown that the general oceanographic parameters studied here influence FeMn crust composition based on their geographic location and water depth, and these parameters can help create criteria for future crust exploration

Mineralogical compositions of sediment samples from the San Francisco Bay coastal system

The mineralogical compositions of 119 samples collected from throughout the San Francisco Bay coastal system, including bayfloor and seafloor, area beaches, cliff outcrops, and major drainages, were determined using X-ray diffraction (XRD). Comparison of the mineral concentrations and application of statistical cluster analysis of XRD spectra allowed for the determination of provenances and transport pathways. The use of XRD mineral identifications provides semi-quantitative compositions needed for comparisons of beach and offshore sands with potential cliff and river sources, but the innovative cluster analysis of XRD diffraction spectra provides a unique visualization of how groups of samples within the San Francisco Bay coastal system are related so that sand-sized sediment transport pathways can be inferred. The main vector for sediment transport as defined by the XRD analysis is from San Francisco Bay to the outer coast, where the sand then accumulates on the ebb tidal delta and also moves alongshore. This mineralogical link defines a critical pathway because large volumes of sediment have been removed from the Bay over the last century via channel dredging, aggregate mining, and borrow pit mining, with comparable volumes of erosion from the ebb tidal delta over the same period, in addition to high rates of shoreline retreat along the adjacent, open-coast beaches. Therefore, while previously only a temporal relationship was established, the transport pathway defined by mineralogical and geochemical tracers support the link between anthropogenic activities in the Bay and widespread erosion outside the Bay. The XRD results also establish the regional and local importance of sediment derived from cliff erosion, as well as both proximal and distal fluvial sources. This research is an important contribution to a broader provenance study aimed at identifying the driving forces for widespread geomorphic change in a heavily urbanized coastal-estuarine system

Deep-ocean mineral deposits as a source of critical metals for high- and green-technology applications: Comparison with land-based resources

Ferromanganese (Fe–Mn) crusts are strongly enriched relative to the Earth's lithosphere in many rare and critical metals, including Co, Te, Mo, Bi, Pt, W, Zr, Nb, Y, and rare-earth elements (REEs). Fe–Mn nodules are strongly enriched in Ni, Cu, Co, Mo, Zr, Li, Y, and REEs. Compared to Fe–Mn crusts, nodules are more enriched in Ni, Cu, and Li, with subequal amounts of Mo and crusts are more enriched in the other metals. The metal ions and complexes in seawater are sorbed onto the two major host phases, FeO(OH) with a positively charged surface and MnO2 with a negatively charged surface. Metals are also derived from diagenetically modified sediment pore fluids and incorporated into most nodules. Seafloor massive sulfides (SMS), especially those in arc and back-arc settings, can also be enriched in rare metals and metalloids, such as Cd, Ga, Ge, In, As, Sb, and Se. Metal grades for the elements of economic interest in SMS (Cu, Zn, Au, Ag) are much greater than those in land-based volcanogenic massive sulfides. However, their tonnage throughout the global ocean is poorly known and grade/tonnage comparisons with land-based deposits would be premature. The Clarion–Clipperton Fe–Mn Nodule Zone (CCZ) in the NE Pacific and the prime Fe–Mn crust zone (PCZ) in the central Pacific are the areas of greatest economic interest for nodules and crusts and grades and tonnages for those areas are moderately well known. We compare the grades and tonnages of nodules and crusts in those two areas with the global terrestrial reserves and resources. Nodules in the CCZ have more Tl (6000 times), Mn, Te, Ni, Co, and Y than the entire global terrestrial reserve base for those metals. The CCZ nodules also contain significant amounts of Cu, Mo, W, Li, Nb, and rare earth oxides (REO) compared to the global land-based reserves. Fe–Mn crusts in the PCZ have significantly more Tl (1700 times), Te (10 times more), Co, and Y than the entire terrestrial reserve base. Other metals of significance in the PCZ crusts relative to the total global land-based reserves are Bi, REO, Nb, and W. CCZ nodules and PCZ crusts are also compared with the two largest existing land-based REE mines, Bayan Obo in China and Mountain Pass in the USA. The land-based deposits are higher grade but lower tonnage deposits. Notably, both land-based deposits have < 1% heavy REEs (HREEs), whereas the CCZ has 26% HREEs and the PCZ, 18% HREEs; the HREEs have a much greater economic value. Radioactive Th concentrations are appreciably higher in the land-based deposits than in either type of marine deposit. A discussion of the differences between terrestrial and marine impacts and mine characteristics is also presented, including the potential for rare metals and REEs in marine deposits to be recovered as byproducts of mining the main metals of economic interest in nodules and crusts

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&ndash;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&ndash;825 m) Fe&ndash;Mn crusts dredged from the summit of RGR by using computed tomography, X-ray diffraction, 87Sr/86Sr ratios, U&ndash;Th isotopes, and various analytical techniques to determine their chemical composition. Fe&ndash;Mn crusts from RGR have two distinct generations. The older one has an estimated age of initiation around 48&ndash;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&ndash;Mn deposits, such as low Fe/Mn ratios (mean 0.52), high Mn, Ni, and Li contents and the presence of a 10 &Aring; 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&ndash;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&ndash;Mn crusts from deeper-water depths along the RGR plateau and surrounding areas, which would less likely be affected by phosphatization

Marine Phosphorites as Potential Resources for Heavy Rare Earth Elements and Yttrium

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

Controls on ferromanganese crust composition and reconnaissance resource potential, Ninetyeast Ridge, Indian Ocean

A reconnaissance survey of Fe–Mn crusts from the 5000 km long (~31°S to 10°N) Ninetyeast Ridge (NER) in the Indian Ocean shows their widespread occurrence along the ridge as well as with water depth on the ridge flanks. The crusts are hydrogenetic based in growth rates and discrimination plots. Twenty samples from 12 crusts from 9 locations along the ridge were analyzed for chemical and mineralogical compositions, growth rates, and statistical relationships (Q-mode factor analysis, correlation coefficients) were calculated. The crusts collected are relatively thin (maximum 40 mm), and those analyzed varied from 4 mm to 32 mm. However, crusts as thick as 80 mm can be expected to occur based on the age of rocks that comprise the NER and the growth rates calculated here. Growth rates of the crusts increase to the north along the NER and with water depth. The increase to the north resulted from an increased supply of Mn from the oxygen minimum zone (OMZ) to depths below the OMZ combined with an increased supply of Fe at depth from the dissolution of biogenic carbonate and from deep-sourced hydrothermal Fe. These increased supplies of Fe increased growth rates of the deeper-water crusts along the entire NER. Because of the huge terrigenous (rivers, eolian, pyroclastic) and hydrothermal (three spreading centers) inputs to the Indian Ocean, and the history of primary productivity, Fe–Mn crust compositions vary from those analyzed from open-ocean locations in the Pacific. The sources of detrital material in the crusts change along the NER and reflect, from north to south, the decreasing influence of the Ganga River system and volcanic arcs located to the east, with increasing influence of sediment derived from Australia to the south. In addition, weathering of NER basalt likely contributed to the aluminosilicate fraction of the crusts. The southernmost sample has a relatively large detrital component compared to other southern NER crust samples, which was probably derived predominantly from weathering of local volcanic outcrops. Fe–Mn crusts from a dredge haul at 3412 m water depth, 2°S latitude, are pervasively phosphatized along with the substrate rocks (site D7). Phosphatization took place through replacement of carbonate, preferential replacement of Fe oxyhydroxide relative to Mn oxide in the crusts, preferential replacement of silica-rich phases relative to Al-rich phases in the crusts, and precipitation of carbonate fluorapatite in pore space. The preferentially replaced silica may have been Si adsorbed on the Fe oxyhydroxide. The enrichment of Ni, Zn, and Cu in the phosphatized crust reflects preferential adsorption into the tunnel structure of todorokite. The rare earth element plus yttrium (REY) patterns indicate a lower oxidation potential during phosphatization of the NER crusts compared to Pacific phosphatized crusts. NER phosphatization occurred in a deeper-water environment than typical for phosphatization of Pacific crusts, occurred post-middle Miocene, a younger age than phosphatization the Pacific crusts, and had in part a different set of chemical changes produced by the phosphatization than did the Pacific crusts. The southern third of NER has Fe–Mn crusts with the highest Co (0.91%), Ni (0.43%), ΣREY (0.33%), Cu (0.22%), Te (146 ppm), Pt (1.5 ppm), Ru (52 ppb), and Rh (99 ppb) contents. These are among the highest Pt, Ru, and Rh concentrations measured in marine Fe–Mn deposits. Because of these high metal concentrations, exploration is warranted for the southern sector of the NER, especially at shallower-water sites where the platinum group elements (PGE) and Co are likely to be even more enriched

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