(Fig 2, page 399), Distribution of Fe and Mn in ferromanganese nodules of the Eningi-Lampi Lake, Russia

The distribution of Mn and Fe in water, sediments, hydroxide nodules and crusts of Eningi-Lampi ore-bearing lake is regular, and concordant from the source to the areas of accumulation of these components. Mn-Fe hydroxide nodules and crusts occur at the water-sediment interface, and more rarely in the upper (0-5 cm) film of brown watery mud. The leading role in the formation of Mn-Fe nodules and crusts is played by the chemosorption and auto-catalytic oxidation in the course of interaction of component-bearing solutions with active surfaces. This is considered to be the basic process for the model of ferromanganese ore formation in recent basins. Despite the differences in the physico-geographical and geochemical characteristics of lakes, mediterranean seas and oceans, the formation of ferromanganese hydroxide nodules and crusts in these basins may be explained by this model.

Manganese oxide minerals: Crystal structures and economic and environmental significance

Manganese oxide minerals have been used for thousands of years—by the ancients for pigments and to clarify glass, and today as ores of Mn metal, catalysts, and battery material. More than 30 Mn oxide minerals occur in a wide variety of geological settings. They are major components of Mn nodules that pave huge areas of the ocean floor and bottoms of many fresh-water lakes. Mn oxide minerals are ubiquitous in soils and sediments and participate in a variety of chemical reactions that affect groundwater and bulk soil composition. Their typical occurrence as fine-grained mixtures makes it difficult to study their atomic structures and crystal chemistries. In recent years, however, investigations using transmission electron microscopy and powder x-ray and neutron diffraction methods have provided important new insights into the structures and properties of these materials. The crystal structures for todorokite and birnessite, two of the more common Mn oxide minerals in terrestrial deposits and ocean nodules, were determined by using powder x-ray diffraction data and the Rietveld refinement method. Because of the large tunnels in todorokite and related structures there is considerable interest in the use of these materials and synthetic analogues as catalysts and cation exchange agents. Birnessite-group minerals have layer structures and readily undergo oxidation reduction and cation-exchange reactions and play a major role in controlling groundwater chemistry.

Heavy metal contents in Fe-Mn nodules and crusts from R/V Vityaz polygons and stations in the East Indian Ocean

Regional variations in abundance, morphology, and chemical composition of Fe-Mn nodules have a zonal character. Due to circumcontinental zonality of terrigenous sedimentation the main mass of the nodules occurs in the pelagic part of the ocean, in areas of minimal sedimentation rates. In spatial variations in morphology and chemical composition of the nodules the latitudinal zonality is very clear and associated with latitudinal changes in facial conditions of sedimentation. Elevated contents of Mn, Ni, and Cu and of Mn/Fe ratio occur in nodules from the radiolarian belt. Changes of chemical composition of the nodules with depth (vertical zonality of mineralization) are confirmed. Local variations in abundance, morphology and chemical composition of the nodules are caused by ruggedness of relief and depth variations, variations in sedimentation rate, age of ore formation, intensity of diagenetic redistribution of metals.

(Table 2) Chemical composition of upper and lower surfaces of Fe-Mn nodules from the Eastern Subequatorial Pacific

Materials of polygon exploration during Cruise 41 of R/V Dmitry Mendeleev showed that diagenetic and sedimentary-diagenetic nodules close in morphology, texture, and composition vary greatly in size and productivity. Local variations in productivity of this nodule type in pelagic areas of the Pacific Ocean are closely connected with thickness of underlying clayey-radiolarian oozes.