TL;DR: In this paper, the same authors employed a combination of mineralogical-geochemical enrichment and geochemical association (defined statistically) signatures, in conjunction with several diagnostic plots, to distinguish between the following different genetic types of manganese deposits: supergene hydrothermal, super gene marine terrestrial; super gionite dubhite; and super gienine marine hydro-thermal sedimentary exhalative (sedex).
Abstract: Manganese oxides have a strong sorption capacity for cationic species in the depositional fluid. This sorption capacity is reflected in the chemistry of the oxides, which is different from that for the oxides precipitated from fresh water, seawater, and hydrothermal fluids. Characteristic mineralogical-geochemical enrichment and geochemical association (defined statistically) signatures, in conjunction with several diagnostic plots, can be employed to distinguish between the following different genetic types of manganese deposits: supergene hydrothermal; supergene marine terrestrial; supergene dubhite; and supergene marine hydrothermal sedimentary exhalative (sedex). "Dubhites" are manganese oxides derived from the weathering of a mineralized sequence (i.e., base and precious ore minerals and gangue). Hydrothermal deposits characteristically show geochemical enrichments in the assemblage As-Ba-Cu-Li-Mo-Pb-Sb-Sr-V-Zn and an Mn-As geochemical association. Supergene marine deposits show Na-K-Ca-Mg-Sr and Co-Cu-Ni geochemical enrichments, whereas supergene terrestrial deposits tend to have very high Ba contents and an Mn-Ba association. Dubhites contain high levels of Pb and Zn, show an Mn-Pb-base metal association, and are composed of significant quantities of base metal-bearing manganese oxides. Bixbyite, braunite, hausmannite, huebnerite, jacobsite, and pyrochroite occur predominantly only in hydrothermal deposits, whereas chalcophanite, coronadite, crednerite, delta -MnO 2 , groutite, hollandite, lithiophorite, manganite, nsutite, quenselite, ramsdellite, romanechite, todorokite, and woodruffite are generally of supergene origin. In addition to established plots presently used to identify marine sedimentary exhalative deposits, the following diagnostic graphs were devised: Na vs. Mg distinguishes deposits of marine and fresh water origin, Co + Ni vs. As + Cu + Mo + Pb + V + Zn discriminates between hydrothermal and supergene oxides, and Pb vs. Zn can be used to recognize dubhites and therefore prospective sequences.
TL;DR: In the presence of Mn(II), ferrihydrite transforms into Mn-goethite and/or jacobsite, and, at high Mn(III) concentrations, a 7-A phyllomanganate as mentioned in this paper.
Abstract: In the presence of Mn(II), ferrihydrite transforms into Mn-goethite and/or jacobsite. Chemical analysis showed that as much as 15 mole % Mn replaced Fe in the goethite structure. If Mn(III) replaced Mn(II), the formation of jacobsite was suppressed; ferrihydrite transformed into Mn-goethite, and, at high Mn(III) concentrations, a 7-A phyllomanganate. Low levels of Mn(II) retarded the transformation of ferrihydrite only slightly, whereas in an Mn(III) system the nucleation and growth of Mn-goethite were both hindered. Mn-goethite nucleated in solution, whereas jacobsite appeared to form by interaction of dissolved Mn(II) species with ferrihydrite. Mn suppressed the formation of hematite in these systems; however, Mn-hematite containing as much as 5 mole % Mn was induced to form at pH 8 by adding oxalate to the system. Transmission electron micrographs showed that goethite crystals grown in the presence of Mn were long (≤2 μm) and thin and commonly contained etch pits. The presence of Mn appears to have promoted twinning.
TL;DR: In this paper, a review of spinel-type structures with the general formula AB 2ϕ4 is presented, where ϕ can be O2−, S2− or Se2−.
Abstract: Compounds with a spinel-type structure include mineral species with the general formula AB 2ϕ4, where ϕ can be O2−, S2−, or Se2−. Space group symmetry is Fd 3 m , even if lower symmetries are reported owing to the off-center displacement of metal ions. In oxide spinels (ϕ = O2−), A and B cations can be divalent and trivalent (“2–3 spinels”) or, more rarely, tetravalent and divalent (“4-2 spinels”). From a chemical point of view, oxide spinels belong to the chemical classes of oxides, germanates, and silicates. Up to now, 24 mineral species have been approved: ahrensite, brunogeierite, chromite, cochromite, coulsonite, cuprospinel, filipstadite, franklinite, gahnite, galaxite, hercynite, jacobsite, magnesiochromite, magnesiocoulsonite, magnesioferrite, magnetite, manganochromite, qandilite, ringwoodite, spinel, trevorite, ulvospinel, vuorelainenite, and zincochromite. Sulfospinels (ϕ = S2−) and selenospinels (ϕ = Se2−) are isostructural with oxide spinels. Twenty-one different mineral species have been approved so far; of them, three are selenospinels (bornhardtite, trustedtite, and tyrrellite), whereas 18 are sulfospinels: cadmoindite, carrollite, cuproiridsite, cuprokalininite, cuprorhodsite, daubreelite, ferrorhodsite, fletcherite, florensovite, greigite, indite, kalininite, linnaeite, malanite, polydymite, siegenite, violarite, and xingzhongite. The known mineral species with spinel-type structure are briefly reviewed, indicating for each of them the type locality, the origin of the name, and a few more miscellaneous data. This review aims at giving the state-of-the-art about the currently valid mineral species, considering the outstanding importance that these compounds cover in a wide range of scientific disciplines.
TL;DR: One of the problems of the wartime program of studies of domestic manganese deposits concerned the identification of, and modes of origin of the menganese oxide minerals as discussed by the authors, was to identify the minerals of about 250 specimens by X-ray analysis; complete chemical analyses were made of about 35 specimens and partial analyses of about 150 specimens.
Abstract: One of the problems of the wartime program of studies of domestic manganese deposits concerned the identification of, and modes of origin of the manganese oxide minerals. Of the hundreds of specimens of the oxides collected in the United States, the minerals of about 250 specimens were identified by X-ray analysis; complete chemical analyses were made of about 35 specimens and partial analyses of about 150 specimens. This report presents the conclusions that arise out of a review of the geologic environment under which the specimens were found. One conclusion of this review concerns the supergene vs. hypogene origin of the oxides. In order to reach conclusions concerning the supergene and hypogene origin of the 33 oxides of manganese recognized thus far, it was necessary to define the criteria that seemed usable.One group of oxides appears to be persistently supergene: groutite, hydrohausmannite, lithiophorite, rancieite, hetaerolite, hydrohetaerolite, chalcophanite, crednerite, woodruffite, and wad. Another group of oxides appears to have been formed only by hypogene processes: manganosite, hausmannite, pyrochroite, bixbyite, galaxite, jacobsite, franklinite, pyrophanite, and ilmenite. A third group of oxides appear to have been formed by supergene processes in some places and by hypogene processes in other places: manganite, pyrolusite, ramsdellite, cryptomelane, psilomelane, hollandite, braunite, and coronadite.Another conclusion concerns a genetic relation between: (1) veins of manganese oxides in the southwest, largely in Tertiary volcanic rocks, (2) bodies of oxides in travertine aprons near active hot springs, and inactive Pleistocene springs, and (3) stratified oxides, largely in late Tertiary sedimentary rocks in the southwest. From the features of these three groups of deposits of oxides and their geologic and geographic distribution, it appears that hot water from great depth rose on fractures in areas of volcanic activity, deposited oxides in the fractures, appeared at the surface as hot springs, deposited oxides in the aprons near the springs and continuing to local basins, deposited manganese oxides with local debris as persistent beds in sediments, partly or wholly of volcanic origin.
TL;DR: In this article, the authors used non-invasive Raman microspectroscopy, FTIR, μXRD and XRF to identify the materials present in the black, red, and white surface decorations in selected pottery wares from two Prehispanic archaeological sites in Northwestern (NW) Argentina (AD 900-1530).