G. V. Novikov

Nature of co-bearing ferromanganese crusts of the Magellan Seamounts (Pacific Ocean): Communication 1. Geology, mineralogy, and geochemistry

Communication 1 of the present paper is devoted to various aspects of the hydrogenic ferromanganese crusts in the western and eastern clusters of the Magellan Seamounts in the Pacific. It was revealed that crusts are developed on guyots as a continuous sheet of Fe-Mn minerals on exposures of primary rocks. They commonly make up ring-shaped deposits along the periphery of the summit surface and in the upper sectors of slopes. Thickness of the crust varies from n to ∼18 cm and shows irregular variations in separate layers. Irrespective of the geographic position, crusts are composed of four layers—two lower phosphatized (I-1 and I-2) and two upper nonphosphatized (II and III) layers. The crusts differ in terms of structure and texture, but they are sufficiently similar within separate layers (I-1, I-2, and others). The major ore minerals in crusts are commonly represented by poorly crystallized and low-ordered minerals (Fe-vernadite and Mn-feroxyhyte); the subordinate mineral, by the well-crystallized and ordered vernadite. It has been established that heavy and rare metal cations are concentrated extremely irregularly in ore minerals of the crusts, suggesting a pulsating mode of their input during different geological epochs.

Synthesis and sorption properties of layered hydrous manganese dioxide saturated with s-, p-, and d-metal cations

Layered compounds based on hydrous manganese dioxide (hereafter, Mn-phases) saturated with s-metal (Ba2+), p-metal (Pb2+), and d-metal (Mn2+, Co2+, Ni2+, Cu2+, Zn2+, and Cd2+) cations, analogues of manganese minerals of oceanic ferromanganese formations (vernadite, birnessite, buserite-I, and asbolan), were prepared at 4–6°C. All Mn-phases have poorly ordered structures. The sorption properties of phase compounds were studied in relation to alkali-metal (Na+ and K+) and other s-, p-, and d-metal cations. The exchange capacities of Mn-phases for alkali cations are very low, within 0.02–0.10 mg-equiv/g; for the other cations, the exchange capacities are 0.13–4.20 mg-equiv/g. The sorption of divalent metal cations depends on the phase and chemical composition of the Mn-phase.

Nature of Co-bearing ferromanganese crusts of the Magellan Seamounts (Pacific Ocean): Communication 2. Ion exchange properties of ore minerals

The results of experimental studies of ion exchange properties of Co-bearing ferromanganese crusts in the Magellan Seamounts (Pacific Ocean) are discussed. Maximum reactivity in reactions with the participation of manganese minerals (Fe-vernadite, vernadite) is typical of Na+, K+, and Ca2+ cations, whereas minimum activity is recorded for cations Pb2+ and Co2+. The exchange complex of ore minerals in crusts is composed of Na+, K+, Ca2+, Mg2+, and Mn2+ cations. The exchange capacity of manganese minerals increases from the alkali metal cations to rare and heavy metal cations. Peculiarities of the affiliation of Co2+, Mn2+, and Mg2+ cations in manganese minerals of crusts are discussed. In manganese minerals, Co occurs as Co2+ and Co3+ cations. Metal cations in manganese minerals occur in different chemical forms: sorbed (Na+, K+, Ca2+, Mn2+, Co2+, Cu2+, Zn2+, Cd2+, and Pb2+); sorbed and chemically bound (Mg2+, Ni2+, Y3+, La3+, and Mo6+); and only chemically bound (Co3+). It is shown that the age of crust, its preservation time in the air-dry state, and type of host substrate do not affect the ion exchange indicators of manganese minerals. It has been established that alkali metal cations are characterized by completely reversible equivalent sorption, whereas heavy metal cations are sorbed by a complex mechanism: equivalent ion exchange for all metal cations; superequivalent, partly reversible sorption for Ba2+, Pb2+, Co2+, and Cu2+ cations, relative to exchange cations of manganese minerals. The obtained results refine the role of ion exchange processes during the hydrogenic formation of Co-bearing ferromanganese crusts.

Mineralogy of morphogenetic types of ferromanganese deposits in the world ocean

The mineralogy and structural features of the main types of ferromanganese deposits—nodules, micronodules, Co-bearing crusts, crustlike nodules, and low-temperature hydrothermal manganese crusts and ferruginous ochers—are considered. The correlation between their mineral composition and structure is shown. The proposed classification of mineral types is based on characteristic assemblages of Fe and Mn minerals.

Ion exchange properties of manganese and iron minerals in oceanic micronodules

The results of experimental studies of ion exchange properties of manganese and iron minerals in micronodules (MN) from diverse bioproductive zones of the World Ocean are considered. It was found that the sorption behavior of these minerals is similar to that of ore minerals from ferromanganese nodules (FMN) and low-temperature hydrothermal crusts. The exchange complex of minerals in the MN includes the major (Na+, K+, Ca2+, Mg2+, and Mn2+) and the subordinate (Ni2+, Cu2+, Co2+, Pb2+, and others) cations. Reactivity of theses cations increases from Pb2+ and Co2+ to Na+ and Ca2+. Exchange capacity of MN minerals increases from the alkali to heavy metal cations. Capacity of iron and manganese minerals in the oceanic MN increases in the following series: goethite < goethite + birnessite < todorokite + asbolane-buserite + birnessite < asbolane-buserite + birnessite < birnessite + asbolane-buserite < birnessite + vernadite Fe-vernadite + Mn-feroxyhyte. The data obtained supplement the available information on the ion exchange properties of oceanic ferromanganese sediments and refine the role of sorption processes in the redistribution of metal cations at the bottom (ooze) water-sediment interface during the MN formation and growth.

Mineralogy and Geochemistry of Co-bearing manganese crusts from the Govorov and Volcanologist guyots of the Magellan Seamounts (Pacific Ocean)

Co-bearing manganese crusts (CMCs) from the Govorov and Volcanologist guyots (Magellan Seamounts, Pacific Ocean) are of the same type and consist of three layers (I-1, II, III) and a “dried crust” variety of layer III. It is shown that the structural and textural pattern are quite similar within individual layers. The major ore minerals of the crusts are poorly crystallized, have a low degree of structural ordering, and include Fe-vernadite, Mn-feroxyhyte, and less abundant, well-crystallized, and structurally ordered vernadite. It is shown that the cations of ore (Со, Ni, Cu), rare, and rare-earth metals are irregularly concentrated in ore minerals of CMCs, which provides evidence for the pulsating nature of their supply at different geological stages.

Sources of Minor and Rare-Earth Elements in Hydrothermal Edifices of Near-Continental Rifts with Sedimentary Cover: Evidence from the Guaymas Basin, Southern Trough

The mineralogy and geochemistry of a fragment of an active hydrothermal edifice from the Hydrothermal Hill of the Southern Trough valley of the Guaymas Basin in the Gulf of California were studied. The sample was collected from a depth of 1995 m by the Pisces manned submersible on cruise 12 of the R/V Akademik Mstislav Keldysh, Institute of Oceanology, Russian Academy of Sciences. The fragment and the edifice itself consists of two accrete pipes: ore (pyrrhotite) and barren (carbonate) combined in a single edifice by an outer barite–opal zone. The ore edifice is located in the rift zone of the Guaymas Basin with a thick sedimentary cover and is depleted in metals in comparison with ores from rift zones of the open ocean, which are not blocked by sedimentary deposits. This is explained by loss of metals at the boundary between hot sills and sedimentary rocks and by the processes of interaction of hydrothermal solutions with sedimentary deposits. The sedimentary series faciitates long-term preservation of endogenous heat and the ore formation process. Ore edifices of the Guaymas Basin are mostly composed of pyrrhotite, have a specific set of major elements, microelements and REEs, and contain naphthenic hydrocarbons. They may be search signs of hidden polymetallic deposits, considered to be the roots of ore occurrences localized under the surface of the bottom in young active rifts with high spreading and sedimentation rates, i.e., in near-continental areas of rifts of the humid zone with avalanche sedimentation.

The Oligocene gap in the formation of Co-rich ferromanganese crusts and sedimentation in the Pacific Ocean and the effects of bottom currents

The Marcus Wake and Magellan guyots formed about 129–74 Ma ago at 10°–30° S and drifted 1700–4400 km to their present-day latitudinal position across the equatorial zone of maximum deposition. Cooling of the Pacific plate brought these guyots to the northern arid zone during the Turonian–Maastrichtian, to depths at which sediment accumulation rates were low and the conditions promoted precipitation of Co-rich Fe–Mn crusts from the Campanian to the present. Nonprecipitation of Co-rich Fe–Mn crusts during the Oligocene was caused by the action of bottom currents. The presence of a hiatus identified in cores from drill holes was used as the basis for reconstruction of the directions of bottom currents in the Oligocene.

Metal cation exchange reactions of ore minerals in Fe–Mn crusts of the Marcus Wake Rise (Pacific Ocean) in aqueous–salt solutions

It is shown that the reaction ability of metal cations of ore minerals in Fe–Mn crusts of the Marcus Wake Rise increases in the following manner: (Co2+ < Cu2+ < Ni2+) < (Mg2+ < Mn2+ < K+ ≈ Ca2+ ≈ Na+). The composition of the exchange complex of the ore minerals is constant and includes these metal cations. Ca2+ and Na+ are major contributors to the exchange capacity of the ore minerals. The capacity of the ore minerals by cations of alkali and base metals is 0.43–0.60 and 2.08–2.70 mg-equiv/g, respectively. The exchange capacity of the ore minerals by cations of base metals increases linearly with the increase in the MnO2 content of the crust and does not depend on the geographical locations of the Marcus Wake guyots.

Behavior of Zn2+, Cd2+, Ba2+ and Pb2+ cations in ferromanganese crusts from the Marcus Wake seamount (Pacific Ocean) in aqueous solutions of metal salts

The behavior of heavy-metal cations in ore minerals of cobalt-rich ferromanganese crusts from the Marcus Wake seamount in aqueous solutions of metal salts was studied in experiments. The Zn2+ and Cd2+ cations showed high reactivity and Ва2+ and Pb2+ showed low reactivity. It was found that Zn2+ and Cd2+ cations within the ore mineral composition are mainly absorbed (up to 66%) whereas Pb2+ and Ва2+ are chemically bound (up to 70%). Ore minerals in the crusts are characterized by sorption properties and high ionexchange capacity by these cations (1.94–2.62 mg-equiv/g). The capacity values by heavy-metal cations for ore minerals of the crusts from different areas of the Marcus Wake seamount are close to each other.