Miscibility and compatibility of braunite,Mn2+Mn 6 3+ O8/SiO4, in the system Mn-Si-O at 1 atm in air

Experimental investigations between 800 ° to 1,100 ° C yielded no evidence for extensive substitution of Mn²⁺+Si⁴⁺2Mn³⁺ in braunite, leading to a complete solid solution series between partridgeite (Mn₂O₃) and braunites with silica contents up to 40 wt. % as proposed by Muan (1959a, b). In the presence of excess manganese braunite of nearly ideal composition coexists at 800 ° C with partridgeite and at T1,000 ° C with hausmannite (Mn₃O₄). At 800 ° C and 1,000 ° C braunite coexists, in the presence of excess silica, with a SiO₂-polymorph and at 1,100 ° C with rhodonite (MnSiO₃). Quantitative analysis of the X-ray patterns of coexisting cristobalite and braunite confirms a maximum silica-excess in braunite of only about 2 wt.% over the ideal composition, Mn²⁺Mn ₆ ³⁺ SiO₁₂.     

Phase relationships of sursassite and other Mn-silicates in highly oxidized low-grade,high-pressure metamorphic rocks from Evvia and Andros islands,Greece

High-pressure, low-temperature metamorphic Mn-rich quartzites from Andros and Evvia (Euboea) islands, Greece, situated in the Eocene blueschist belt of the Hellenides, reveal different Mn-Al-Ca-Mg-silicate assemblages in response to variable metamorphic grade. On Evvia, piemontite- and/or braunite-rich quartzites which are associated with low-grade blueschists (T<400° C, P> 8 kbar) show the principle mineral assemblage quartz + montite + sursassite + braunite + Mg-chlorite + hematite + rutile + titanite. The Mn-Al-silicate sursassite, basically (Mn²⁺, Ca)₄ Al₂(Al, Fe³⁺, Mn³⁺, Mg)₄Si₆O₂₁(OH)₇, thus far reported as a rare mineral, locally occurs as a rockforming mineral in cm- to m-thick layers. On Andros, higher-grade quartzites (T450–500° C, P>10 kbar) of similar composition contain the assemblage quartz + piemontite + spessartine + braunite + Mg-chlorite+hematite + phengite+ phlogopite + rutile. Rare sursassite is present only as a relict phase. Additional, mostly accessory minerals in quartzites from Evvia and Andros are ardennite, Na-amphibole, acmitic clinopyroxene, albite, apatite, and tourmaline. The chemical composition of the main phases is characterized in detail.Disequilibrium textures and mineral compositions in some samples from Andros and Evvia imply the reactions sursassite + braunite + quartz = spessartine+clinochlore±hematite + H₂O + O₂ (1) sursassite + braunite + phengite + quartz = spessartine + phlogopite±hematite + H₂O + O₂ (2) and in braunite-free assemblages sursassite + Mn³⁺Fe _–1 ³⁺ [hematite, piemontite] + hematite + quartz = spessartine + clinochlore + H₂O+O₂ (3) Reactions (1) to (3) have positive P-T slopes. They are considered to account for the breakdown of sursassite and the formation of spessartine during prograde metamorphism of the piemontite quartzites and related rocks. P-T data from Andros and Evvia and geological data from few other occurrences reported suggest sursassite+ quartz±braunite to be stable at T<400–450° C over a considerable pressure interval at least up to 10 kbar. Theoretical phase relations among Mn³⁺-Mn²⁺-silicates in the pseudoquaternary system Al-Mn-Ca-Mg with excess quartz, H₂O, and O₂ indicate that low-grade assemblages containing sursassite (±braunite±pumpellyite±viridine±piemontite + quartz) are likely precursors of higher-grade assemblages including spessartine, Mg-chlorite, braunite, viridine, and piemontite reported from greenschist-, amphibolite-, and high-grade blueschist-facies rocks of appropriate composition.     

Geochemistry of braunite and associated phases in metamorphosed non-calcareous manganese ores of India

In the metamorphosed manganese oxide ores of India, braunite is ubiquitous in all assemblages from chlorite to sillimanite grades. Chemical analyses of braunite from different prograde assemblages confirm the presence of a fixed R²⁺ (=Mn²⁺+Mg+Ca) SiO₃ molecule in the mineral. Element partitioning between coexisting braunite and bixbyite indicates a near-ideal mixing of Fe⁺³/ -Mn⁺³ in the phases. This also indicates that braunite became relatively ferrian while equilibrating with associated phases such as bixbyite, hollandite and jacobsite during prograde reactions. Petrogenetic studies show that as a general trend, prograde lower oxide phases appeared by deoxidation of higher oxide phases. But braunite, a more reduced phase than bixbyite, appeared early from deoxidation of pyrolusite in presence of quartz. Bixbyite could appear later from the reacting pyrolusite-braunite-quartz assemblage. Inferred mineral reaction paths and the general trend of pro-grade deoxidation reactions suggest that the composition of ambient fluid phase was internally buffered during metamorphism.     

Magnetic phase diagrams of Mg-, Fe-, (Cu + Ti)- and Cu-substituted braunite Mn<Superscript>2+</Superscript>Mn<Subscript>6</Subscript><Superscript>3+</Superscript>SiO<Subscript>12</Subscript>

 The magnetic behavior of the Jahn-Teller structure braunite, (Mn²⁺ _1−yM _y )(Mn³⁺ _{6− x} M_x)SiO₁₂, is strongly influenced by the incorporation of elements substituting manganese. Magnetic properties of well-defined synthetic samples were investigated in dependence on the composition. The final results are presented in magnetic phase diagrams. To derive the necessary data, ac susceptibility and magnetization of braunites with the substitutional elements M = Mg, Fe, (Cu+Ti) and Cu were measured. Whereas the antiferromagnetic ordering temperature, T _N , of pure braunite is hardly affected by the substitution of nonmagnetic Mg, it is rapidly suppressed by the substitution of magnetic atoms at the Mn positions. Typically for a concentration (x, y) ≥ 0.7 of the substituted elements, a spin glass phase occurs in the magnetic phase diagrams. Additionally, for the braunite system with Fe³⁺ substitutions, we observe in the concentration range 0.2 < x< 0.7 a double transition from the paramagnetic state, first to the antiferromagnetic state, followed by a transition to a spin glass state at lower temperatures. The unusual change of the magnetic properties with magnetic substitution at the Mn positions is attributed to the peculiar antiferromagnetic structure of braunite, which has been resolved recently. Received: 19 April 2001 / Accepted: 6 September 2001     

Origin and metamorphic evolution of rocks with braunite and pyrophanite from the Iberian Massif (SW Spain)

Summary ?Rocks containing braunite from the Ossa-Morena central belt (Iberian Massif, SW Spain) have been studied; these include nodules and layers of braunite (association I), Mn-slates (association II) and Mn-metatuffs (associations III and IV). Geochemical features of braunite nodules such as Mn/Fe ratios around 2, positive Ce-anomalies and good correlations among Mn, Fe, Co, Cu and REE contents indicate that the protolith of the braunite-nodules was precipitated from oxidising sea water. Greenschist facies Hercynian metamorphism reduced initial Mn⁴⁺ to Mn³⁺ and Mn²⁺. High initial fO₂ of oxide beds (association I) limited reduction to the formation of braunite. Reduction continued until the formation of garnet + piemontite (associations II and III), and pyroxmangite + pyrophanite (association IV). Ti-rich braunites (up to 6.8% of TiO₂) occur in slates and metatuffs in which the (Mn + Fe)/Ti ratio of the whole rock is lower than 30, while braunites have lower Ti contents in slates and metatuffs with (Mn + Fe)/Ti ratios around 90. Fe-rich braunite crystallized in rocks with Mn²⁺ oxide and silicate where low Mn³⁺/Mn²⁺ in the whole rock facilitated substitution of Fe³⁺ for Mn³⁺. Received January 30, 2002; revised version accepted May 7, 2002 Published online November 22, 2002     

Minerals of the viridine hornfels from Darmstadt,Germany

Viridine containing the highest amounts of Mn₂O₃ detected thus far (up to 20.5 mol % “Mn₂SiO₅”) coexists in a metasedimentary hornfels with spessartine, Mn-phlogopite (mangan-ophyllite), Mn-phengite (alurgite), hematite, quartz and probably some primary braunite. In layers poorer in viridine spessartine is absent but piemontite appears as an additional phase. Microprobe analyses of all these phases are presented which indicate very strong fractionation of Mg and Mn in coexisting phlogopite and garnet, and of Fe and Mn in coexisting hematite and braunite. Sericitic aggregates consisting of phengitic muscovite and braunite are interpreted as retrograde alteration products of viridine, but might partly be pinitic alterations of a former Mg-rich cordierite. Due to the occurrence of the assemblage spessartine-viridine-quartz Mn-cordierite cannot have been a stable phase prior to retrograde alterations. In general the stability field of viridine is extended towards higher temperatures as compared to that of pure andalusite, Al₂SiO₅. Due to the coexistence of phlogopite and muscovite (phengite) the temperature of contact metamorphism cannot have exceeded some 550°–650° C depending on the prevailing water pressure.     

Composition and formation of fossil manganese nodules in Jurassic to Cretaceous radiolarites from the Nicoya Ophiolite Complex (NW Costa Rica)

Horizons of several types of Upper Jurassic to Lower Cretaceous manganese nodules occur locally in sequences of radiolarian cherts within the Nicoya Ophiolite Complex (NW Costa Rica). Field studies, X-ray diffraction analysis, petrographic, chemical and experimental studies give evidence of a sedimentary, early diagenetic origin of the nodules, in contrast to earlier suggestions. Smooth, discoidal, compact and very dense nodules with diameters of some mm to 9 cm dominate. They are characterized by braunite, hollandite, pyrolusite and quartz as well as 39–61% Mn, 0.9–1.6% Fe, 5–26% SiO₂, 1.3–1.9% A1₂O₃, 1.5–3.0% Ba, 460–5400 ppm Cu, 85–340 ppm Ni and 40–130 ppm Co, among others. It is suggested that the original mineralogy (todorokite?) was altered during thermometamorphic (braunite) and hydrothermal (hollandite, pyrolusite) events. Petrographic similarities between the fossil nodules and modern deep-sea nodules are striking. Using standard hydrothermal techniques in an experimental study it is shown that under special conditions, braunite can be produced from modern nodule material.     

Quelques caractéristiques des faciès à oxydes de manganèse dans le gisement de St. Marcel-Praborna — V. Aoste,Italie

Résumé La braunite du gisement de St. Marcel-Praborna, dans le Val d'Aoste (Italie) présente un certain nombre de faciès et générations caractéristiques. Chacun de ces faciès possède non seulement des particularités morphologiques mais aussi des traits géochimiques propres.La braunite en filigrane représente la première génération de braunite dans le gisement et certains de ses traits géochimiques semblent hérités des séries originelles.Le faciès de braunite compacte représente la braunite presque pure, tandis que la braunite en filigrane renferme tout à la fois du Ca, du Fe, du Ti, ainsi que des traces en éléments de transition (Ni notamment).L'importance de la teneur en MnO₂ du gisement nous parait étroitement liée à l'enrichissement tardif en K⁺ du gisement.Les rapports paragénétiques et l'évolution des oxydes manganésifères de St. Marcel sont des traits que l'on retrouve dans les oxydes des nodules polymétalliques ayant subi les effets du métamorphisme.L'oxydation des silicates et carbonates, souvent due aux fracturations tardives, est négligeable dans ce gisement.

---

Braunite in the metamorphosed Mn ore-body at St. Marcel-Praborna Val d'Aosta, Italy, occurs in several textural forms, each characterised by particular morphological or chemical features.Sponge-like (filigran-texture) braunite contains Ca, Fe, Ti and traces of some transition elements, especially Ni. This form represents the first braunite generation in this deposit and some of its chemical features are inherited by its transformation products.A second generation of braunite is compact and idioblastic and has almost the pure end-member chemical composition.The significant MnO₂ content of this deposit seems to be closely related to a late enrichment in K.The paragenetic relationships and the evolution of the Mn-oxides of St. Marcel have the characteristics of oxides in those polymetallic nodules which have been metamorphosed.Oxidation of silicates and carbonates, often due to late fracturing, is negligible in this deposit.

     

Crystal chemistry and reaction relations of piemontites and thulites from highly oxidized low grade metamorphic rocks at Vitali,Andros Island,Greece

Piemontite- and thulite-bearing assemblages from highly oxidized metapelitic and metacalcareous schists associated with braunite quartzites at Vitali, Andros island, Greece, were chemically investigated. The Mn-rich metasediments are intercalated in a series of metapelitic quartzose schists, marbles, and basic metavolcanites which were affected by a regional metamorphism of the highP/T type (T=400–500° C,P>9 kb) and a later Barrovian-type greenschist metamorphism (T=400–500° C,P～-5–6 kb). Texturally and chemically two generations of piemontite (I and II) can be distinguished which may show complex compositional zoning. Piemontite I coexisted at highP/T conditions with braunite, manganian phengite (alurgite), Mn³⁺-Mn²⁺-bearing Na-pyroxene (violan), carbonate, quartz, hollandite, and hematite. Zoned grains generally exhibit a decreasing Mn³⁺ and an increasing Fe³⁺ and Al content towards the rim. Chemical compositions of piemontite I range from 2.0 to 32.1 mole % Mn³⁺, 0 to 25.6 mole % Fe³⁺, and 60.2 to 81.2 mole % Al. Up to 12.5 mole % Ca on the A(2) site can be substituted by Sr. Piemontites formed in contact or close to braunite (±hematite) attained maximum (Mn³⁺+Fe³⁺)Al_?1 substitution corrresponding to about 33 mole % Mn³⁺+Fe³⁺ in lowiron compositions and up to about 39 mole % Mn³⁺+ Fe³⁺ at intermediate Fe³⁺/(Fe³⁺+Mn³⁺) ratios. Piemontite II which discontinuously overgrows piemontite I or occurs as separate grains may have been formed by greenschist facies decomposition of manganian Na-pyroxenes according to the reaction: (1) $$\begin{gathered} {\text{Mn}}^{{\text{3 + }}} - Mn^{2 + } - bearing omphacite/chloromelanite \hfill \\ + CO_2 + H_2 O + HCl \pm hermatite \hfill \\ = piemontite + tremolite + albite + chlorite \hfill \\ + calcite + quartz + NaCl \pm O_2 . \hfill \\ \end{gathered} $$ Thulites crystallized in coexistence with Al-rich piemontite II. All thulites analysed are low-Fe³⁺ manganian orthozoisites with Mn^tot～-Mn³⁺ substituting for Al on the M(3) site. Their compositions range from 2.9 to 7.2 mole % Mn³⁺, 0 to 1.2 mole % Fe³⁺, and 91.8 to 96.7 mole % Al. Piemontites II in thulite-bearing assemblages range from 5.8 to 15.9 mole % Mn³⁺, 0 to 3.7 mole % Fe³⁺, and 83.7 to 93.6 mole % Al. By contrast, piemontites II in thulite-free assemblages are similarly enriched in Mn³⁺ + Fe³⁺ — and partially in Sr²⁺ — as core compositions of piemontite I (21.1 to 29.6 mole % Mn³⁺, 2.0 to 16.5 mole % Fe³⁺, 60.6 to 68.4 mole % Al, 0 to 29.4 mole % Sr in the A(2) site). The analytical data presented in this paper document for the first time a continuous low-Fe³⁺ piemontite solid solution series from 5.8 to 32.1 mole % Mn³⁺. Aluminous piemontite II is enriched by about 3 mole % Mn³⁺+Fe³⁺ relative to coexisting thulite in Fe³⁺-poor samples and by about 6 mole % Mn³⁺+Fe³⁺ in more Fe³⁺-rich samples. Mineral pairs from different samples form a continuous compositional loop. Compositional shift of mineral pairs is attributed to the effect of a variable fluid composition at constantP _fluid andT on the continuous reaction: (2) $$\begin{gathered} piemontite + CO_2 \hfill \\ = thulite + calcite + quartz \hfill \\ + Mn^{2 + } Ca_{ - 1} [calcite] + H{_2} O + O{_2} \hfill \\ \end{gathered} $$ Further evidence for a variable \(x_{H_2 O} \) and/or \(f_{O_2 } \) possibly resulting from fluid infiltration and local buffering during the greenschist metamorphism is derived from the local decomposition of piemontite, braunite, and rutile to form spessartine, calcite, titanite, and hematite by the reactions: (3) $$\begin{gathered} piemontite + braunite + CO_2 \hfill \\ = sperssartine + calcite + quartz \pm hermatite \hfill \\ + H{_2} O + O{_2} \hfill \\ \end{gathered} $$ and more rarely: (4) $$\begin{gathered} piemontite + quartz + rutile + braunite \hfill \\ = spessartine + titanite + hematite + H{_2} O + O{_2} . \hfill \\ \end{gathered} $$      

Découverte de microstructures de nodules polymétalliques dans les minéralisations manganésifères métamorphiques de Falotta et de Parsettens (Grisons-Suisse)

Résumé Les minéralisations manganésifères de Falotta et de Parsettens (Grisons-Suisse) se manifestent dans les radiolarites du Jurassique supérieur et elles sont déposées sur les ophiolites du domaine pennique. Ce minerai présente des microstructures botryoïdales caractéristiques des nodules polymétalliques. Les phases minéralogiques des nodules, sous l'effet du métamorphisme alpin, se transforment de façon progressive en braunite faiblement cristallisée (avec un important excès en SiO₂) à la périphérie des structures botryoïdales; par contre, vers la partie centrale de ces structures, la braunite est souvent largement cristallisée (sa teneur en SiO₂ est normale). De fines veinules constituées de termes intermédiaires de la série isostructurale de la cryptomélanehollandite recoupent la minéralisation de braunite et indiquent la deuxième étape dans l'évolution du minerai oxydé de Falotta et Parsettens. La troisième étape est représentée par la présence de la todorokite et de la birnessite due à l'oxydation des veinules postérieures de rhodonite. Ces deux oxydes n'ont aucun rapport direct avec la minéralisation primaire. L'existence de structures sédimentaires et volcaniques non déformées dans les écailles supérieures de la nappe de Platta permet d'expliquer la conservation de microstructures primaires de nodules polymétalliques dans le minerai de braunite. La variation de la teneur en Sr²⁺ observée lorsque l'on va de Falotta vers Parsettens, dans les termes intermédiaires de la série isostructurale de la cryptomélane-hollandite, ainsi que la déstabilisation de la braunite au voisinage des veinules, seraient liées à la différence du degré de déformation entre ces deux zones. Il est important de remarquer que les paramètres géochimiques Fe/Mn ou Mn/Co&+Cu&+Ni, couramment utilisés dans les travaux sur les nodules polymétalliques, sont inadéquats même dans les structures les mieux préservées.

---

The manganese ores of Falotta and Parsettens (Oberhalbstein, Grison Canton, Switzerland) are enclosed in Upper Jurassic radiolarites and overlay ophiolites of Upper Pennine nappes. These ores exhibit the botryoidal microstructures typical of manganese nodules. The mineralogical components of the outerpart of these nodules, which were affected by alpine metamorphism — were first transformed gradually into a poorly crystallized braunite (with a large excess of SiO₂). In contrast, the inner part of the nodules is composed of well-crystallized braunite with normal (10 wt%) contents of SiO₂. Narrow veinlets with intermediate members of the cryptomelane-hollandite isostructural series crosscut the braunite mineralization, and represent a secondary paragenesis. A third step is marked by the appearance of todorokite and birnessite through the oxidation of the rhodonite veinlets. This is apparently the first observation of primary botryoidal microstructures in these nodules — and the first observation of braunite microstructures in a metamorphic area. The occurrence of undeformed volcanic and sedimentary textures in the upper Platta thrust sheets explains the preservation of these primary structures in these nodules. Moreover, the increase in flattening and intensive schistosity from Falotta to Parsettens may be related with the enrichment of Sr²⁺ in the intermediate members of the cryptomelane-hollandite series and with the destabilization of the braunite along the veinlets. It must also be pointed out that the Fe/Mn or Mn/Co&+Cu&+Ni ratios, currently used in research on manganese nodules, seem to be inadequate even for the Falotta ore, in which the best-preserved primary microstructures exist. In Falotta as in Parsettens, todorokite and birnessite come from the late rhodonite veinlets and are not related with the primary ore.

     

The mineralogy and petrology of manganese-rich rocks from St. Marcel,Piedmont, Italy

Manganese-rich metamorphic rocks containing violan from St. Marcel, Piedmont, Italy formed under blueschist facies conditions, yielding an unusual suite of minerals including omphacite-albite-quartz, braunite, microcline, hollandite, piedmontite, and strontian calcite. Violan, a violet-colored pyroxene, is shown to be a manganoan omphacite having a primitive unit cell, and is found in the same sample as diopside, possibly indicating a solvus relation. A manganoan phlogopite and a celadonitic muscovite coexist in one sample with microcline. The occurrence of celadonite and phlogopite is the first from the blueschist facies and the celadonite component in the dioctahedral mica is buffered at a maximum by coexistence with phlogopite, microcline, and quartz. Various phase relations are used to establish the P and T of equilibration at 8±1 kbar and 300±50 °C, respectively, while the oxygen fugacity is shown to have been very high, for these temperatures, as consistent with braunite+quartz and the presence of piedmontite. Contribution No. 343, from the Mineralogical Laboratory, Department of Geology and Mineralogy, The University of Michigan, Ann Arbor, MI 48109, USA     

Structural control of polyhedral compression in synthetic braunite, Mn2+Mn3+ 6O8SiO4

The compression of synthetic braunite, Mn²⁺Mn³⁺ ₆O₈SiO₄, was studied by high-pressure single-crystal X-ray diffraction carried out in a diamond-anvil cell. The equation of state at room temperature (third-order Birch-Murnaghan equation of state: V ₀=1661.15(8) ų, K _0,298=180.7±0.9 GPa, K′=6.5±0.3) was determined from unit-cell volume data to 9.18 GPa. Crystal structures were determined at 6 different pressures to 7.69 GPa. Compression of the structure (space group I4₁/acd) was found to be slightly anisotropic (a ₀=9.4262(4) Å, K _a =499±4 GPa, K _a ′=19.7±0.9; c ₀=18.6964(6) Å, K _c =657±6 GPa, K _c ′=15.7±1.4) which can be attributed to the fact that the Mn³⁺-O bonds, which are the most compressible bonds, are aligned closer to the (001) plane than to the c axis. The large bulk modulus is the result of the structural topology in which 2/3 and 1/2 of the edges of the Mn²⁺O₈ and Mn³⁺O₆ polyhedra share edges with other polyhedra. The Mn²⁺O₈ polyhedra were found to compress isotropically, whereas anisotropic compressional behaviour was observed for all three Mn³⁺O₆ octahedra. Although the polyhedral geometry of all three crystallographically independent Mn³⁺ sites shows the same type of uniaxially elongated distortion, the compression of the individual octahedral configurations was found to be strongly dependent upon both the geometry of the polyhedron itself and the types of, and the connectivity to, the neighbouring polyhedra. The differences in the configuration of the different oxygen atoms, and therefore the structural topology, is one of the major factors determining the type and degree of the pressure-induced distortion, while the Jahn-Teller effect plays a subordinate role.     

Manganese oxide mineralogy,petrography and genesis,Pilbara Manganese Group,Western Australia

Supergene manganese oxides, occurring in shales, breccias and dolomites of Proterozoic Age, in the Western Australian Pilbara Manganese Group, have Mn/Fe ranging from 1.9 to 254 and Mn⁴⁺ to Mn (Total) of 0.49–0.94. The manganese mineralogy is dominated by tetravalent manganese oxides, especially by cryptomelane, with lesser amounts of pyrolusite, nsutite, manjiroite, romanechite and other manganese oxide minerals. The manganese minerals are commonly associated with iron oxides, chiefly goethite, indicating incomplete separation of Mn from Fe during Tertiary Age arid climate weathering of older, manganiferous formations. These manganese oxides also contain variable amounts of braunite and very minor hausmannite and bixbyite. The braunite occurs in three generations: sedimentary-diagenetic, recrystallised sedimentary-diagenetic, and supergene. The mode of origin of the hausmannite and bixbyite is uncertain but it is possible that they resulted from diagenesis and/or low-grade regional metamorphism. The supergene manganese deposits appear to have been derived from manganiferous Lower Proterozoic banded iron formations and dolomites of the Hamersley Basin and overlying Middle Proterozoic Bangemali Basin braunite-containing sediments.     

Pink manganian phengite in a high P/T meta-conglomerate from northern Syros (Cyclades, Greece)

A new occurrence of Mn-rich rocks was discovered within the high-pressure/low-temperature metamorphic rocks on the Palos peninsula of Syros (Greece). Near the summit of Mount Príonas, a meta-conglomerate consists of calcite (~63 wt%), pink manganian phengite, blue–purple manganian aegirine–jadeite, microcline, albite and quartz. In addition, it contains abundant braunite-rich aggregates (up to ~1.5 cm in diameter) that include hollandite [(Ba_0.98–1.02K_<0.01Na_<0.02Ca_<0.03) (Mn _1.02–1.52 ³⁺ Fe _0.38–0.88 ³⁺ Ti_0.29–0.92Mn _5.11–5.76 ⁴⁺ )O₁₆], barite and manganian hematite. Due to metamorphic recrystallization and deformation, the contacts between clasts and matrix are blurred and most clasts have lost their identity. In back-scattered electron images, many aegirine–jadeite grains appear patchy and show variable jadeite contents (Jd_10–67). These pyroxenes occur in contact with either quartz or albite. Manganian phengite (3.41–3.49 Si per 11 oxygen anions) is of the 3T type and contains 1.4–2.2 wt% of Mn₂O₃. At the known P–T conditions of high-pressure metamorphism on Syros (~1.4 GPa/ 470 °C), the mineral sub-assemblage braunite + quartz + calcite (former aragonite) suggests high oxygen fugacities relative to the HM buffer (+7 ≤ ?f_O2 ≤ + 17) and relatively high CO₂ fugacities. The exact origin of the conglomerate is not known, but it is assumed that the Fe–Mn-rich and the calcite-rich particles originated from different sources. Braunite has rather low contents of Cu (~0.19 wt%) and the concentrations of Co, Ni and Zn are less than 0.09 wt%. Hollandite shows even lower concentrations of these elements. Furthermore, the bulk-rock compositions of two samples are characterized by low contents of Cu, Co and Ni, suggesting a hydrothermal origin of the manganese ore. Most likely, these Fe–Mn–Si oxyhydroxide deposits consisted of ferrihydrite, todorokite, birnessite, amorphous silica (opal-A) and nontronite. Al/(Al + Fe + Mn) ratios of 0.355 and 0.600 suggest the presence of an aluminosilicate detrital component.     

Origin of a carbonate-hosted Fe-Mn-(Ba-As-Pb-Sb-W) deposit of Långban-type in central Sweden

The Sjögruvan deposit is one of the Långban-type Fe-Mn oxide deposits hosted by marble interbeds within Svecofennian metavolcanic rocks in the Bergslagen region, central Sweden. Mineralogical and geochemical studies have been carried out to clarify the premetamorphic origin of this type of deposit, which is set apart from most other Mn mineralizations by a significant enrichment in Ba, As, Sb, Pb, W and Be contained by various oxyminerals. The principal ore types at Sjögruvan are (1) hematite+quartz-magnetite, (2) hausmannite+calcite+tephroite and (3) braunite+celsian+phlogopite. The Mn ores are compositionally akin to modern Mn deposits formed by submarine hydrothermal processes (with a high Mn/Fe ratio and low contents of Co, Ni, Th, U and REE) and likely owe their existence to similar mechanisms of formation. Pb isotope data indicate that the metal source and timing of deposition is similar to the major stratabound base-metal and iron deposits in Bergslagen. All the key elements have been leached from the local felsic volcanic units and were deposited on the sea floor; the excellent Mn-Fe separation occurred in an Eh-pH gradient that essentially corresponded to the mixing zone of hydrothermal solutions and seawater. The braunite ore is chemically distinct from the hausmannite ore, with a high concentration of refractory elements (Al, Ti, Zr) and a positive Ce anomaly, which indicate a detrital/hydrogenetic contribution to its protolith. Carbon isotope ('¹³C) values around 0‰ (relative PDB) suggest that carbonates in the deposit formed directly from seawater.     

A Talc--Phengite Assemblage in Piemontite Schist from Brezovica, Serbia, Yugoslavia

Talc occurs in direct contact with phengite in a manganiferousschist containing piemontite, spessartine, quartz, chlorite,hematite, braunite, and occasional phlogopite. The resultingtalc-phengite tie line in the AKF plot is a novelty for bothnatural rocks and the synthetic model system K₂O-MgO-Al₂O₃-SiO₂-H₂Owhich contains about 95 per cent of the components making upthe four phyllosilicates present in the schist. The remainingcomponents are CuO, MnO, and minor Fe₂O₃, CoO, NiO in the chlorite,talc, and phlogopite, as well as Fe₂O₃ in the phengite. Two possibilities for the origin of the talc-phengite assemblageare discussed: 1. The presence of the components CuO etc. in the phyllosilicatesprovides additional degrees of freedom or causes shifts of reactioncurves in the synthetic model system thus creating a hypotheticalnew invariant point at intermediate pressures allowing a talc-phengitefield. 2. The rock was formed under very high water pressures whichpermit the coexistence of talc and phengite even in the puresynthetic system according to a theoretical prediction of phaserelations from limited experimental data available.     

Tephroite-hausmannite-galaxite from a granulite-facies manganese rock of the United Arab Emirates

The assemblage tephroite-hausmannite_ss-galaxite_ss has been found in a granulite-facies manganese ore body associated with metabasites and quartzrich lithologies. The metamorphic rocks are located in the Khawr Fakkan massif near the northern end of the Semail Ophiolite, United Arab Emirates (U.A.E.), metamorphosed at 800–850°C and 6.5–9 kbar. The galaxite shows approximately 35% solid solution of hausmannite, similar to that reported for jacobsite and franklinite whereas the solid solution of galaxite in hausmannite is maximally 7%. The assemblage of tephroite-hausmannite and hausmannite-galaxite indicates a restricted log fO₂ of-9 to-11 which is outside the stability of braunite under similar physico-chemical conditions. The modal abundance of the minerals and bulk rock chemistry indicate that the present assemblage was formed from the breakdown of Fe-poor braunite_ss+hausmannite_ss.     

Mineralogy,paragenesis and genesis of the braunite deposits of the Mary Valley Manganese Belt,Queensland, Australia

The Mary Valley manganese deposits exhibit mineralogy and textures characteristic of at least four parageneses. The deposits consist mainly of isolated occurrences of braunite, together with a number of lower and higher valency manganese oxides, and manganese silicates, in bedded radiolarian cherts and jaspers of Permian age. The parageneses are: (a) Braunite — quartz (primary), (b) Braunite — hausmannite — spessartine — tephroite — quartz (metamorphic). (c) Hydrated manganese silicates — barite — braunite — hausmannite (hydrothermal veins), (d) Tetravalent manganese oxides (pyrolusite, cryptomelane, manjiroite, nsutite) (supergene). The primary mineralisation is interpreted as the result of the geochemical separation of Mn from Fe in a submarine exhalative system, and the precipitation of Mn as oxide within bedded radiolarian oozes and submarine lavas. During diagenesis this hydrothermal manganese oxide reacted with silica to produce primary braunite. The later geological of evolution of this volcanogenicsedimentary deposit involved metamorphism, hydrothermal veining by remobilised manganese, and supergene enrichment.     

Hollandite–strontiomelane solid solutions coexisting with kanonaite and braunite in late quartz veins of the Stavelot Massif, Ardennes, Belgium

In a newly found type of quartz vein cross-cutting the famous "viridine"-bearing phyllites at Le Coreux, hollandite, ideally BaMn₈O₁₆, was discovered for the first time at this locality and in Belgium. Because the crystals contain up to 60 mol% of the Sr end member, this is also the second occurrence of strontiomelane. The coexisting "viridine" (= kanonaite) contains the highest amount (88 mol%) of the ideal end member MnAlSiO₅ ever found worldwide. The hollandite-type minerals are intimately intergrown with braunite containing appreciable Ca and Mg. Ba-bearing muscovite, Fe-poor excess-Al clinochlore (not quite trioctahedral), and albite are the remaining accessory minerals in the dominant quartz matrix. Microprobe analyses of all phases show rather extreme element fractionations: nearly all K is located in muscovite and none in the hollandite phase despite the existence of the end member KMn₈O₁₆ (cryptomelane). Similarly, nearly all Na is in albite and not in hollandite (no NaMn₈O₁₆=manjiroite component). Nearly all Mn resides in the two oxide phases and in kanonaite. Mg is strongly fractionated into chlorite. The small amounts of Fe and Ti present are predominantly partitioned into the hollandite phase, which also accommodates most of the Ba and Sr. Indeed, the hollandite phase is stabilized by the latter two elements relative to other Mn oxides. Kanonaite is stabilized by Al. Although no requisite sites are available in its crystal structure, braunite always contains small amounts of Ba and Sr. However, the Sr/(Sr+Ba) ratios in braunite are spurious and unrelated to those of the directly adjoining hollandite phases The conditions of formation of these veins may be well below 300 °C at low pressures (1-2 kbar), in agreement with the experimental results that the maximum Mn contents in kanonaite increase with falling temperatures.     

Chloritoid stability in manganese rich low-grade metamorphic rocks,Venn-Stavelot Massif,Ardennes

The Southern Venn-Stavelot Massif is characterized by Ordovician and Devonian rocks very rich in manganese and aluminum, which are attacked by a low grade regional metamorphism. The assemblages 1 (phengite, paragonite, chlorite, chloritoid, garnet, quartz, hematite, rutile) and 2 (phengite, paragonite, chlorite, kaolinite (andalusite, pyrophyllite), garnet, quartz, hematite, rutile) are of basic interest for the formation of chloritoid. As the two rock types are isofaciell and quasi-identical in chemistry except for the iron oxides, there is clear evidence for the influence of on the chloritoid formation at its lower p-T stability limit. This can be shown by a discussion of the phase relations of chloritoid, garnet, kaolinite, chlorite and phengite in respect to the oxidation ratio mol 2 Fe₂O₃x 100/2 Fe₂O₃+ FeO of the host rocks. Especially chloritoid and chlorite change their chemistry in a characteristic way with rising oxidation ratio in getting richer and richer in manganese and magnesium (chloritoid) and magnesium (chlorite). A simultaneous increase in trivalent iron in these phases is supposed. At an oxidation ratio of 85–90 the stability limit of chloritoid is reached. The increasing substitution of manganese and magnesium up to this limit should have a stabilizing effect. In a rough estimate the oxygen partial pressure is supposed to be in the order of 10⁻¹⁰ atm at the stability limit of chloritoid assuming a temperature of metamorphism between 360–400° C. Rocks with oxidation ratios between 90 and 100 are characterized by the presence of kaolinite. If the oxidation ratio is still higher (all iron as Fe³⁺, parts of the manganese in the trivalent state), the rocks belong to assemblage 3 (phengite, paragonite, chlorite, viridine, (kaolinite), (garnet), quartz, hematite, braunite, rutile). Dedicated to Prof. Dr. K. Jasmund at his 60. birthday.