(Table 1, page 171) Thorium and cobalt content of the total aggregate of manganese nodules from various locations

A criterion is suggested for discrimination between ferromanganese oxide minerals, deposited after the introduction of manganese and associated elements in sea water solution at submarine vulcanism, and minerals which are slowly formed from dilute solution, largely of continental origin. The simlultaneous injection of thorium into the ocean by submarine vulcanism is indicated, and its differentiation from continental thorium introduced into the ocean by runoff is discussed.

(Table 1, page 1376) Chemical analyses of manganese nodules and crusts from the Pacific Ocean

A compilation of chemical analyses of Pacific Ocean nodules using an x-ray fluorescence technique. The equipment used was a General Electric XRD-5 with a tungsten tube. Lithium fluoride was used as the diffraction element in assaying for all elements above calcium in the atomic table and EDDT was used in conjunction with a helium path for all elements with an atomic number less than calcium. Flow counters were used in conjunction with a pulse height analyzer to eliminate x-ray lines of different but integral orders in gathering count data. The stability of the equipment was found to be excellent by the author. The equipment was calibrated by the use of standard ores made from pure oxide forms of the elements in the nodules and carefully mixed in proportion to the amounts of these elements generally found in the manganese nodules. Chemically analyzed standards of the nodules themselves were also used. As a final check, a known amount of the element in question was added to selected samples of the nodules and careful counts were taken on these samples before and after the addition of the extra amount of the element. The method involved the determination and subsequent use of absorption and activation factors for the lines of the various elements. All the absorption and activation factors were carefully determined using the standard ores. The chemically analyzed samples of the nodules by these methods yielded an accuracy to at least three significant figures.

(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 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.

(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.

(Table II, page 668-669) Distribution of elements between minerals soluble in 1M Hydroxylamine hydrochloride (Reducible); in 1m HCL (Acid-soluble) and in the insoluble residue of manganese nodules

Attempts to classify pelagic sediments have been based either on appearance and composition, or on the ultimate origin of the components. In particular it appears feasible to distinguish minerals which crystallized in sea-water from those which formed in magmas, in hydrothermal solution, or by weathering under acidic conditions. It is the case of iron and manganese oxide mineral aggregates which constitute one of the major types of rock encountered on the ocean floor; according to Menard (unpublished) about 10% of the pelagic area of the Pacific is covered by such nodules. The nodules consist of intimately intergrown crystallites of different minerals among those identified, besides detrital minerals and organic matter, are opal, goethite, rutile, anatase, barite, nontronite, and at least three manganese oxide minerals of major importance. Arrhenius and Korkisch (1959) have attempted to separate from each other the different minerals constituting the nodules, in order to establish the details of their structure and the localization of the heavy metal ions. The results demonstrate (Table II) that copper and nickel are concentrated in the manganese oxide phases concentrated in the reducible fraction. Cobalt, part of the nickel and most of the chromium are distributed between these and the acid-soluble group of the non-manganese minerals, dominated by goethite and disordered FeOOH.

Study on the hydrolysis/precipitation behavior of Keggin Al-13 and Al-30 polymers in polyaluminum solutions

The hydrolysis/precipitation behaviors of Al3+, Al-13 and Al-30 under conditions typical for flocculation in water treatment were investigated by studying the particulates' size development, charge characteristics, chemical species and speciation transformation of coagulant hydrolysis precipitates. The optimal pH conditions for hydrolysis precipitates formation for AlCl3, PAC(A113) and PAC(A130) were 6.5-7.5, 8.5-9.5, and 7.5-9.5, respectively. The precipitates' formation rate increased with the increase in dosage, and the relative rates were AlCl3 >> PAC(A130) > PACA113. The precipitates' size increased when the dosage increased from 50 mu M to 200 mu M, but it decreased when the dosage increased to 800 AM. The Zeta potential of coagulant hydrolysis precipitates decreased with the increase in pH for the three coagulants. The isoelectric points of the freshly formed precipitates for AlCl3, PAC(A113) and PAC(A130) were 7.3, 9.6 and 9.2, respectively. The Zeta potentials of AlCl3 hydrolysis precipitates were lower than those of PAC(A113) and PAC(A130) when pH > 5.0. The Zeta potential of PAC(A130) hydrolysis precipitates was higher than that of PACA113 at the acidic side, but lower at the alkaline side. The dosage had no obvious effect on the Zeta potential of hydrolysis precipitates under fixed pH conditions. The increase in Zeta potential with the increase in dosage under uncontrolled pH conditions was due to the pH depression caused by coagulant addition. Al-Ferron research indicated that the hydrolysis precipitates of AlCl3 were composed of amorphous AI(OH)3 precipitates, but those of PACA113 and PACA130 were composed of aggregates of Al-13 and Al-30, respectively. Al3+ was the most un-stable species in coagulants, and its hydrolysis was remarkably influenced by solution pH. Al-13 and Al-30 species were very stable, and solution pH and aging had little effect on the chemical species of their hydrolysis products. The research method involving coagulant hydrolysis precipitates based on Al-Ferron reaction kinetics was studied in detail. The Al species classification based on complex reaction kinetic of hydrolysis precipitates and Ferron reagent was different from that measured in a conventional coagulant assay using the Al--Ferron method. The chemical composition of Al-a, Al-b and Al-c depended on coagulant and solution pH. The Al-b measured in the current case was different from Keggin Al-13, and the high Alb content in the AlCl3 hydrolysis precipitates could not used as testimony that most of the Al3+ Was converted to highly charged Al-13 species during AlCl3 coagulation.