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By Tobias Hens, Andrew Frierdich, Barbara Etschmann, Joël Brugger, Barrie Bolton

"Ferromanganese (Fe-Mn) nodules and crusts are prime targets for future deep-sea mining ventures due to their unusual enrichment of critical metals, such as Ni, Co, Cu, Ti, Te, Zr, Hf, Nb, Y, and REE. These metals are used in an ever increasing variety of high- and green-tech applications such as alloys, batteries for hybrid cars, fiber-optic cables, or liquid-crystal displays.1 Recovery and processing of these deposits will most likely be cost-intensive and require new solutions.2 Thus, innovative approaches towards the development of sustainable metallurgical processes represent one component that can positively affect the marine mining value chain. Dynamic mineral recrystallization of Fe- Mn oxide phases is a geochemical process that may have notable potential for future hydrometallurgical applications.Our research focuses on Mn oxides – potent trace metal scavengers with high sorptive capacity3 – and biogeochemical mechanisms that control Fe-Mn nodule and crust formation, alteration, and trace element enrichment. Biogeochemical redox cycling of Mn is characterized by microbial oxidation of aqueous Mn(II) to Mn(III,IV) oxides and (a)biotic reduction of these oxides to Mn(II)aq. During this cycling dissolved Mn(II) is in direct contact with solid-phase Mn(III,IV) oxides and can back-react via abiotic pathways (e.g., 4 and references therein). This results in continuous dynamic recrystallization of the Mn mineral substrate through coupled dissolution (trace metal release) – reprecipitation (trace metal incorporation) processes.4 We recently demonstrated in new experiments, that Ni is cycled during manganite recrystallization. It has been shown that, although Ni readily undergoes mineral-fluid repartitioning in the absence of Mn(II)aq, dissolved Mn(II) significantly catalyzes Ni exchange between solid phase and solution. Over a period of 50 days about 30 percent of the Ni atoms in Ni-substituted manganite (natural abundance composition) were exchanged with a 62Ni(II)aq isotope tracer at pH 7.5. Based on these outcomes we employed similar techniques to investigate the impact of dynamic recrystallization on Mn oxide phases in deep-sea ferromanganese nodules and crusts from three circum-Australian locations (South Tasman Rise, Lord Howe Rise, Coral Sea) and the Central Pacific Basin."

Jan 1, 2017

By Delphine Pierre, Jean-Marie Augustin, Anne-Sophie Alix, Charline Guérin, Cecile Cathalot, Yves Fouquet, Arnaud Gaillot, Ewan Pelleter, Carla Scalabrin, Florian Besson

With the world’s growing demand for metals, seafloor massive sulfides (SMS) deposits are now seen as a possible mineral resource that could contributes to secure metal supply for human needs. SMS deposits are characterized by high concentrations of base metals and at some place high contents of precious and rare metals. Since 1977 and the discovery of the first high temperature (HT) hydrothermal vent and its sulfide mineralization and high biodiversity, more than 300 sites are known today. If the exploration strategy for detection of active hydrothermal sites is now robust, their associated mineralization will not (and must not) constitute a potential target for deep-sea mining due to environmental concerns and technical limitations. Recent studies on SMS deposits are rather focused on extinct and buried mineralized sites characterized by a lower biomass. Several geophysical techniques to explore and detect extinct SMS (eSMS) and buried SMS (bSMS) have been developed (e.g. Kawada and Kasaya, 2017; Szitkar et al., 2017, 2014) using different approaches (e.g. regional or local scale; ship-based or using underwater vehicles) with several degrees of success or limitation. Here we present results from acoustic surveys performed on the TAG hydrothermal district during the BICOSE (2014) and LEVE-SMF (2016) cruises and direct observation provided by HOV (Nautile) dives carried out during HERMINE cruise (2017). Acoustic data were acquired using two different multibeam echosounders (MBES): the hull-mounted Kongsberg EM122 (12 kHz, R/V L’Atalante) and the ROV-mounted RESON SeaBat 7125 (400 kHz, ROV Victor) (Figure 1). After processing, acoustic seafloor backscatter data from both MBES provides complementary qualitative results in relation to the seafloor composition. The analysis of the seafloor backscatter data obtained by near-seafloor surveys with the high-resolution 400 kHz MBES shows a clear relationship between low backscatter strength values and areas covered with pelagic and hydrothermal sediments whereas high backscatter strength values are associated to pillow lavas and basaltic scree. Intermediate backscatter strength values are rather related to old and younger eSMS as well as to mineralization on TAG active mound.

Jan 1, 2018

By Alexander Malahoff

Mineral zonation studies were conducted on hydrothermal vents of two hot spot volcanoes. One study site is located within the Axial Caldera of the axial hot spot volcano of the Juan de Fuca Ridge. The young high-temperature hydrothermal vent field consisting of two polymetallic sulfide chimneys, five meters high, located at 130°01.5'W, 45°56.5'N, along a fault complex at the base of the southwestern wall of Axial Caldera was sampled during four ALVIN dives in 1983. Temperatures of up to 270°C were measured within the orifice of one of the chimneys, which was then broken off and recovered with the submersible. Both black and white "smoke" was observed to be emanating from the one chimney sampled. The high-temperature chimney extends directly from a field of broken lobate lavas which are located at a water depth of 1,550 meters, about 200 meters east of the caldera wall. The chimney makes one of the shallowest active high-temperature vents studied to date. The vent is surrounded by clumps of vestimentiferan worms and is located within an elongate field of red-colored iron smectite blankets and chimneys. The low-temperature field forms a ribbon 150 meters wide, extending for about 1,300 meters at the base of the wall. Chemical analyses of the hydrothermal deposits ranging from the polymetallic sulfides of the chimney to the outer zones of the low-temperature field show a range of elemental assemblages consistent with temperature zonation around the vent. Chemical zonation within the high-temperature

Jan 1, 1988

By Wilhelm Schwarz

Manganese nodules lay in vast areas of the deep sea floor. Ideal harvesting conditions for a manganese nodule field are dense nodule abundances of nodules between 20 and 60 mm diameter and a metal content as high as possible. With regard to the development of collector technology, the properties of the deep sea soil, in which the nodules are embedded and to which the nodules stick, are of major interest. The forces for loosening the nodules have to be provided by the collector. For this purpose water jets and/or mechanical devices can be employed. For the choice of the best collecting procedure, various criteria, such as collecting rate, energy consumption and the environmental impact on the eco system of the deep sea floor, have to be considered and weighted as to their importance. Nowadays, the concept of a mining system with a flexible transport hose and a self propelled collecting machine is increasingly accepted among the expert community. With regard to the trafficability of the deep sea soil with a self propelled mining machine, the mechanic properties of the soil and the morphology of the deep sea floor are of special importance. The manganese nodule fields, which are interesting with regard to their recoverability, are mostly in the areas of tectonic fracture zones, at which the morphology of the sea floor is formed by vulcanic activities. In these areas, deep sea mountains, pits and other obstacles exist that have to be driven around if not trafficable.

Jan 1, 2003

By Peter E. Halbach

The Central Indian Ridge (CIR), the boundary between the African and Indian plates, forms a SSE trending mid-oceanic accretionary system in the equatorial Indian Ocean (Fig. 1), extending to the northerly Carlsberg Ridge spreading center, and terminating at the Rodrigues Triple Junction (RTJ; 25°30'S, 70°06'E) by intersection with the Southwest Indian Ridge (SWIR) and the Southeast Indian Ridge (SEIR). Crustal divergence of the CIR proceeds at intermediate rates; a progressive increase of ocean floor accretion towards the south is documented: the present half spreading rate and ridge trend change from 1.80 cm/a and N142° at the equator to 2.73 cm/a and N152° north of the triple point. The topography of the central rift zone is rather smooth compared to slow spreading analogues such as the SWIR, but slightly more rugged than the SEIR. The rift valley is 500-800 m deep, 10-15 km wide and usually well defined. The inner floor, 2-4 km in width, is relatively flat along the axis and more variable in cross section, and lies at 2700-3200 m depth. Off set fracture zones striking generally N60° . in southern portions of the CIR and laterally displacing median valleys by as much as 8 km are often bent, uplifting crustal sequences up to several hundred meters. The length of individual spreading segments varies between a few and several tens of kilometers. The vertical displacement on normal faults are larger while lineaments are shorter than those of the faster spreading SEIR. The direction of lineaments measured on the southwestern and northeastern flanks of the southern CIR are N154° and

Jan 1, 1994

By S. Rajendran

The western continental margin comprises of the southwest coast (Cape Comorin-Mangalore), centralwest coast or Konkan coast (Mangalore-Bombay), northwest coast (Bombay-Gulf of Kutch) and the Laccadives area. Placer deposits of heavy minerals occur in discontinuous patches on the beaches along many parts of the west coast. The richest offshore placer deposits occur along the 25 km stretch of the southwest coast from Neendakara to Kayamkulam. The National Institute of Oceanography (NIO) surveys show that the sediments off the Konkan coast consist largely of silty sand, sandy silt and clay and the concentration of ilmenite is higher than the onshore. The heavy mineral concentration ranges up to 90% and has mainly ilmenite and magnetite with minor quantities of apatite, rutile, zircon, kyanite etc. The heavy mineral sands extend below the clays to water depth down to 20 m. The heavy minerals sands vary in thickness from 2-10 m. Offshore placers can be mined by using wire-line, bucket ladder and hydraulic dredges. Wire-line, bucket ladder and hydraulic dredges. Wire-line dredges may employ drag buckets or clamshell and hydraulic dredges suction or airlift principles. The dredges can be located on flat bottom or catamaran barges. Dredging of very near shore placers may be achieved by operating from land. The bucket ladder type of dredger has greater digging ability and hence can be deployed for mining placers which are partly consolidated or cemented or where the most valuable part of the deposit lies at the contact between the alluvium and the bedrock. This type operates very economically up to 45 m depth and needs minimum power requirement per unit dredged. Suction type hydraulic dredges can be operated very effectively up to 60 m water depths. This system is quite ideal for the inner shelf. The maximum practical economic working water depths for wire-line dredges are about 150 m. With the drag bucket modified into large net buckets, the method can be utilized to greater depths. They can be used in areas of high water currents and swells. The type of bucket can be changed readily with change in the nature of alluvium or substratum. The hydraulic suction dredge is the most suitable system for mining unconsolidated sediments. When the sediments are semi-unconsolidated, a cutter head can be mounted on the lower end of the suction pipe to agitate the seabed.

Jan 1, 1996

By Cornel E. J. de Ronde

Brothers volcano (34°51.7?S, 179°03.6?E) is a large caldera volcano that forms part of the active Kermadec arc south of 32° S, NE of New Zealand. It is an elongate edifice striking NW-SE that is ~11-13 km long by 7-8 km across. The caldera has a basal diameter of 3-3.5 km and is surrounded by 350-450 m high walls with the floor 1,850 m deep. A volcanic cone of dacite composition rises 350 m from the caldera floor and partially coalesces with the southern caldera wall. Much of the caldera construction and the location of the hydrothermal vent sites are controlled by intersecting basement structures. Three hydrothermal sites have been recognized at Brothers; NW caldera, SE caldera and cone. Multiple hydrothermal plumes were mapped from the bottom of the caldera upwards to a depth of 900 m and originate from two of the sites; one on the NW caldera wall the other atop the cone. Analyses of these plumes show that the two vent sites are chemically distinct. The cone site itself hosts three distinct vent fields (summit, upper flank, NE flank) that in 1999 had plumes (mainly from the summit) containing relatively high concentrations of gas with a shift of -0.27 pH units (proxy for CO2) and H2S concentrations up to 4,250 nM, particulate Cu (PCu) of 3.4 nM, total dissolvable Fe (TDFe) of 4,720 nM, TDMn up to 260 nM and Fe/Mn values between 4.4 and 18.2. However, in 2002 plumes from the summit vent field had noticeably lower concentrations of PCu (0.3 nM), TDFe (175 nM), and Fe/Mn values of 0.8, although similar TDMn (220 nM) and shift in pH (-0.22) suggesting a state of flux for this site. By contrast, plumes originating from the NW caldera site have much less gas with a pH shift of -0.09 units and no detectable H2S, TDFe up to 955 nM, TDMn up to 150 nM, and Fe/Mn values of 6.4, and have not changed their composition over the same three year interval indicating a more chronic hydrothermal system. Plume d3He results show helium is decoupled from more near-surface vent fluid sources although a shift in R/Ra values from 6.1 ± 0.5 in 1999 for the combined vent sites to 7.2 ± 0.1 in 2002 indicates a less radiogenic input of helium over three years, suggestive of a greater magmatic input to the system.

Jan 1, 2004

By Peter E. Halbach, Andreas Jahn

Co-rich hydrogenetic ferromanganese crusts are typical marine interface products of growth processes taking place on sediment-free substrate rocks on the seafloor. They grow very slowly and preferentially in water depths below the oxygen-minimum zone (OMZ) and have so far been found even in water depths of up to more than 5000 m, i.e. also below the calcite compensation depth (CCD); these deep ferromanganese crusts are particularly rich in Fe. It is assumed that the O2-minimum zone is the most important source layer of dissolved manganese, the decomposition of fecal pellets here also contributes to this Mn-budget. The process of hydrogenetic precipitation is basically an inorganic colloidal-chemical as well as a surface-chemical mechanism. Microbial mediations can be assumed, in particular since steps of redox-reactions are involved. The two main components of the hydrogenetic substance are hydrated d-MnO2 (vernadite) and x-ray amorphous Fe-oxyhydroxide, both of which are intimately intergrown with each other forming the extremely fine-grained hydrous oxidic material. In seawater, elements occur as dissolved hydrated ions or as inorganic as well as organic complexes which, in general, have either a positive or a negative surface charge depending on the pH of the respective marine environment. These complexes form hydrated colloids that interact with each other or with other dissolved hydrous metal ions. The main agent to oxidize the dissolved Mn2+ ions is oxygen, transported upwards from deeper water by turbulent eddy diffusion and turbulent rise processes at seamount slopes.

Jan 1, 2017