(Table 1, page 754) Estimated concentrations of various elements in nineteen manganese nodules

Using spectrochemical techniques Fe, Si, Mg, Co, Ni, Cu, V, Mo, Ti and Tl have been estimated in nineteen manganese nodules, eight from the Atlantic ocean, seven from the Pacific ocean and four from the Indian ocean. Though data on more samples are required before firm and detailed conclusions can be made about the distribution of elements in manganese nodules, several distinct features appear when the data on the nineteen samples are examined. Certain elements appear to enrich more strongly than others. For example, relative to igneous rocks Mo is much more strongly enriched than V. For several elements (Ni, Cu and particularly Co and Tl) the degree of enrichment in two Fe-low nodules is far smaller than in the other nodules. The magnitude of dispersion of concentration appears to vary considerably for different elements; thus, whereas variation of concentration of V is relatively small, that of Ni, Cu, Co and Tl is far larger. The statistical nature of the distribution of Fe in manganese nodules appears to be characteristic and different from that of the other elements studied so far. Of the possible inter-element relationships examined that of Ni-Cu appears to be the most strongly developed.

(Table, page 351-359) Chemical composition of manganese nodules and crusts from the Pacific and Indian Ocean

Chemical and mineralogical analyses of manganese nodules from a large number of widely spaced localities in the Pacific and Indian Oceans have shown that their mineralogy and chemical composition varies both areally and with depth of formation. This is considered to result from a number of factors, important among which are: (a) their proximity to continental or volcanic sources of elements; (b) the chemical environment of deposition, including the degree of oxygenation; and (c) local factors such as the upward migration of reduced manganese in sediments from certain areas. Sub-surface nodules appear to share the chemical characteristics of their surface counterparts, especially those from volcanic areas where sub-surface sources of elements are probably important.

(Table 1) Chemical composition of Central Pacific manganese micronodules containing birnessite as a major component

Detailed mineralogical characterization of micronodules is given. The main regularities of variations in composition of micronodules from Central Pacific sedimentary rocks of different ages are revealed. New data on structure and structural features of manganese minerals are reported.

Description and composition iron-manganese concretions from the Pacific

One the most interesting features of ocean sedimentation is the manganese formations on the surface of the ocean floor in some areas. These are especially widespread in the Pacific Ocean as concretions, grains, and crusts on rock fragments and bedrock outcrops. Iron-manganese concretions are the most abundant as they completely cover about 10% of the bottom of the Pacific Ocean where there are ore concentrations. The concretions occupy from 20-50% of the bottom and up to 80-90% on separate submarine rises. Such concretions are found in different types of bottom deposits, from abyssal red clays to terrigenous muds, but they occur most widely in red clays and quite often in carbonate muds. Their shape and their dimensions are very diverse and change from place to place, from station to station, varying from 0.5-20 cm. They may be oval, globular, reniform, or slaggy and often they are fiat or isometric concretions of an indefinite shape. The concretions generally have nuclei of pumice, basalt fragments, clayey and tuffaceous material, sharks' teeth, whale ossicles, and fossil sponges. Most concretions have concentric layers, combined with dendritic ramifications of iron and manganese oxides.

(Table 2, page 2172) Chemical analytical data on thirty-two manganese nodules and crusts

Mn, Fe, Ca, Co, Ni, Cu, Zn, Cd, Sn, Tl, Pb and Bi have been estimated in thirty-two nodules from the Pacific, Atlantic and Indian oceans. Various features about the composition of manganese nodules are discussed: element abundances, degrees of enrichment, inter-element relationships (notably between Ni and Cu, and between Zn and Cd), regional variations and some aspects of statistical distribution.

Observation of manganese nodules and crusts recovered during the CHAIN 115 cruise from Nov 1973 until June 1974 in the Atlantic Ocean

Investigations of piston cores from the Vema Channel and lower flanks of the Rio Grande Rise suggest the presence of episodic flow of deep and bottom water during the Late Pleistocene. Cores from below the present-day foraminiferal lysocline (at ~4000 m) contain an incomplete depositional record consisting of Mn nodules and encrustations, hemipelagic clay, displaced high-latitude diatoms, and poorly preserved heterogeneous microfossil assemblages. Cores from the depth range between 2900 m and 4000 m contain an essentially complete Late Pleistocene record, and consist of well-defined carbonate dissolution cycles with periodicities of ~100,000 years. Low carbonate content and increased dissolution correspond to glacial episodes, as interpreted by oxygen isotopic analysis of bulk foraminiferal assemblages. The absence of diagnostic high-latitude indicators (Antarctic diatoms) within the dissolution cyclss, however, suggests that AABW may not have extended to significantly shallower elevations on the lower flanks of the Rio Grande Rise during the Late Pleistocene. Therefore episodic AABW flow may not necessarily be the mechanism responsible for producing these cyclic events. This interpretation is also supported by the presence of an apparently complete Brunhes depositional record in the same cores, suggesting current velocities insufficient for significant erosion. Fluctuations in the properties and flow characteristics of another water mass, such as NADW, may be involved. The geologic evidence in core-top samples near the present-day AABW/NADW transition zone is consistent with either of two possible interpretations of the upper limit of AABW on the east flank of the channel. The foraminiferal lysocline, at ~4000 m, is near the top of the benthic thermocline and nepheloid layer, and may therefore correspond to the upper limit of relatively corrosive AABW. On the other hand, the carbonate compensation depth (CDD) at ~4250 m, which corresponds to the maximum gradient in the benthic thermocline, is characterized by rapid deposition of relatively fine-grained sediment. Such a zone of convergence and preferential sediment accumulation would be expected near the level of no motion in the AABW/NADW transition zone as a consequence of Ekman-layer veering of the mean velocity vector in the bottom boundary layer. It is possible that both of these interpretations are in part correct. The "level of no motion'' may in fact correspond to the CCD, while at the same time relatively corrosive water of Antarctic origin may mix with overlying NADW and therefore elevate the foraminifera] lysocline to depths above the level of no motion. Closely spaced observations of the hydrography and flow characteristics within the benthic thermocline will be required in order to use sediment parameters as more precise indicators of paleo-circulation.

(Plate 3) Manganese nodules and deep-sea sediment core from Pacific Ocean

A synoptic review of the studies of well-known occurrences of palagonite tuffs is presented. Included are palagonite tuffs from Iceland, and pillow-lava palagonite complexes from Columbia River basalts and from the central Oregon coast. Additional petrologic and x-ray defraction data for selected samples are presented. Petrologic evidence shows that basaltic glass of aqueous tuffs and breccias consists of sideromelane, which is susceptible to palagonitization. It is shown that palagonitization is a selective alteration process, involving hydration, oxidation and zeolitization. Some of the manganese nodules dredged from the Pacific Ocean floor contain nucleus of palagonite-tuff breccias or of zeolite. A brief megascopic and microscopic description of nodules from the south Pacific, the Mendocino ridge and the 'Horizon' Nodule from the north Pacific is presented. Petrographic studies of palagonite-tuff breccias of manganese nodules and other palagonites suggest that migration and segregation of metallic elements occur during and subsequent to palagonitization. During the palagonitization of sideromelane, nearly 30 percent of sea water is absorbed. The hydration of sideromelane is also accompanied by oxidation of iron and other elements. These oxides may be released either in colloidal form or in true solution and tend to precipitate first from the unstable palagonite.

(Table 1) Iron and manganese speciations in surface layer bottom sediments of the Pacific Ocean

Distribution of iron and manganese speciations in ocean sediments of a section from the coast of Japan to the open Pacific Ocean is under consideration. Determinations of total iron, as well as of reactive iron contents and of total manganese, as well as of Mn4+ contents have been done. Significant increase of total Fe content in sediments from the coast to the pelagic zone occurs without noticeable increase in reactive Fe content. Presence of layers of volcanic and terrigenous coarse clastic material in clayey sediments results to sharp change in iron content. Manganese content increases from near coastal to pelagic sediments more than 10 times; oxidation degree of sediments also increases. There are three types of bottom sediments different by contents of iron and manganese forms: reduced, oxidized (red clay), and transitional. Content of total Fe is almost does not change with depth in sediments, content of reactive Fe increases in reduced sediments, and decreases in oxidized ones. Manganese content in red clay mass increases several times.

Chemical composition of a manganese nodule from the Tiki Basin, Touamotou Archipelago, Pacific Ocean

The text studies the deep-sea red clays in the East-Central Pacific ocean (Tahiti-Touamotou Archipelago), their authigenic formation, transport and diagenetic character in particular through their composition in REE.

The relationship among serum levels of manganese superoxide dismutase and mtDNA 8-hydroxy-2'-deoxyguanosine, and dietary antioxidants intake in Type 2 Diabetes

Oxidative stress plays a key role in the development of Type 2 Diabetes (T2D). This cross-sectional study examined the relationship among serum levels of manganese superoxide dismutase (MnSOD), 8-hydroxy-2’-deoxyguanosine (8OHdG), dietary antioxidant intakes and glycemic control in African Americans (n=209) and Haitian Americans (n=234) with and without T2D. African Americans had higher BMI (32.8 vs. 29.3 kg/m2), higher energy intake (2148 vs. 1770 kcal), and were more educated as compared to Haitian Americans; all variables were significant at p < .001. Serum levels of 8OHdG and MnSOD for African Americans (1691.0 ± 225.1 pg/ml, 2538.0 ± 1091.8 pg/ml; respectively) were significantly higher than for Haitian Americans (1626.2 ± 222.9, 2015.8 ± 656.3 pg/ml; respectively). 8OHdG was negatively correlated with MnSOD (r = -.167, p < .001) in T2D. Having T2D was negatively correlated with MnSOD (r = -.337; p < .01) and positively correlated with 8OHdG (r = .500; p < .01). African Americans and Haitian Americans with T2D had fasting plasma glucose (FPG) levels of 143.0 ± 61.0 mg/dl and 157.6 ± 65.5 mg/dl, and A1C of 7.5 ± 1.8 % and 8.4 ± 2.4 %, respectively. African Americans and Haitian Americans without T2D had FPG levels of 95.8 ± 13.2 mg/dl and 98.7 ± 16.9 mg/dl, and A1C of 5.9 ± 0.4% and 6.0 ± 0.5%, respectively. Dietary intakes of vitamin C and vitamin D were negatively correlated with FPG (r = -.21; r = -.19, p < .05) respectively. Carotenoids negatively correlated with A1C (r = -.19, p < .05). Lower levels of MnSOD were associated with lower levels of zinc, r = .10, p < .05, and higher levels of carotenoids r = -.10, p < .05. Higher levels of 8OHdG were associated with lower levels of Vitamin D, r = -.14, p < .01, and carotenoids, r = -.09, p < .05. The results demonstrate greater oxidative mtDNA damage in persons with T2D compared to those without T2D and in African Americans compared with Haitian Americans. The inverse relationship between dietary intake of antioxidants and oxidative stress implies a potential to reduce oxidative stress with diet. African Americans were significantly younger (53.3 vs. 55.6 years), had higher BMI (32.8 vs. 29.3 kg/m2), higher energy intake (2148 vs. 1770 kcal), and were more educated as compared to Haitian Americans; all variables were significant at p < .001. Serum levels of 8OHdG and MnSOD for African Americans (1691.0 ± 225.1 pg/ml, 2538.0 ± 1091.8 pg/ml; respectively) were significantly higher than for Haitian Americans (1626.2 ± 222.9, 2015.8 ± 656.3 pg/ml; respectively). 8OHdG was negatively correlated with MnSOD (r = -.167, p < .001) in T2D. Having T2D was negatively correlated with MnSOD (r = -.337; p < .01) and positively correlated with 8OHdG (r = .500; p < .01). African Americans and Haitian Americans with T2D had fasting plasma glucose (FPG) levels of 143.0 ± 61.0 mg/dl and 157.6 ± 65.5 mg/dl, and A1C of 7.5 ± 1.8 % and 8.4 ± 2.4 %, respectively. African Americans and Haitian Americans without T2D had FPG levels of 95.8 ± 13.2 mg/dl and 98.7 ± 16.9 mg/dl, and A1C of 5.9 ± 0.4% and 6.0 ± 0.5%, respectively. Dietary intakes of vitamin C and vitamin D were negatively correlated with FPG (r = -.21; r = -.19, p < .05) respectively. Carotenoids negatively correlated with A1C (r = -.19, p < .05). Lower levels of MnSOD were associated with lower levels of zinc, r = .10, p < .05, and higher levels of carotenoids r = -.10, p < .05. Higher levels of 8OHdG were associated with lower levels of Vitamin D, r = -.14, p < .01, and carotenoids, r = -.09, p < .05. The results demonstrate greater oxidative mtDNA damage in persons with T2D compared to those without T2D and in African Americans compared with Haitian Americans. The inverse relationship between dietary intake of antioxidants and oxidative stress implies a potential to reduce oxidative stress with diet.

(Table 8, page 38) Spectrographic analyses of deep sea manganese nodules from the Pacific and Indian Oceans

In an earlier paper by two of the authors the conclusion was reached that the 33 recognized species of oxides of Mn could be separated into 3 groups: 1) those which appeared to be persistently supergene in origin, 2) those which appeared to be persistently hypogene, and 3) those which were supergene in some localities and hypogene in other localities. When that paper was written, there were available about 250 X-ray diffraction analyses of mineral specimens, also 35 complete and about 150 partial chemical analyses. The conclusions of that paper were based upon the interpretation of the geologic conditions under which these specimens occurred. Late in the preparation of that paper, it seemed worthwhile to make numerous semiquantitative analyses of specimens, largely from 9 western [U.S.A] states, selected carefully from 5 groups of geologic environments, in the hope that the frequency and percentages of some elements might be distinctive of the several geologic groups. For this purpose, 95 specimens were selected from the 5 groups, as follows: 19 specimens interpreted as supergene oxides by the geologists who collected them, 35 specimens of hypogene vein oxides, 22 specimens of Mn-bearing hot spring aprons, 9 specimens of stratified oxides, and 10 specimens of deep-sea nodules. The spectrographic analyses here recorded indicate that a group of elements - W, Ba, Sr, Be, As, Sb, Tl, and Ge - are present more commonly, and largely in higher percentages, in the hypogene oxide than in the supergene oxides and thus serve to indicate different sources of the Mn. Also, the frequency and percentages of some of these elements indicate a genetic relation of the manganese oxides in hypogene veins, hot spring aprons, and stratified deposits. The analyses indicate a declining percentage of some elements from depth to the surface in these 3 related groups and increasing percentages of some other elements. It is concluded that some of the elements in deep-sea nodules indicate that sources other than rocks decomposed on the continents, probably vulcanism on the floors of the seas, have contributed to their formation.