Metamorphic manganese mineralization bound to the metacarbonate lenses at the Smolník – Malá Hekerová deposit in the Spišsko-gemerské rudohorie Mts., Western Carpathians (Slovakia)

Metamorphic manganese mineralization bound to the metacarbonate lenses at the Smolník – Malá Hekerová deposit in the Spišsko-gemerské rudohorie Mts., Western Carpathians (Slovakia) | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Metamorphic manganese mineralization bound to the metacarbonate lenses at the Smolník – Malá Hekerová deposit in the Spišsko-gemerské rudohorie Mts., Western Carpathians (Slovakia) PAVOL MYŠĽAN, MARTIN ŠTEVKO, JIŘÍ SEJKORA, PETER RUŽIČKA, TOMÁŠ MIKUŠ This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6072303/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 03 Jun, 2025 Read the published version in Mineralogy and Petrology → Version 1 posted 7 You are reading this latest preprint version Abstract Metamorphic manganese mineralization recently studied at the Smolník – Malá Hekerová deposit is located within the Early Paleozoic metamorphic volcano-sedimentary sequences of the Bystrý potok Formation, Gelnica Group of the Gemeric Unit, in the Spišsko-gemerské rudohorie Mountains, eastern Slovakia. The manganese mineralization is closely associated with metacarbonate bodies, where Mn-rich calcite, spessartine, titanite, stilpnomelane, fluorapatite and pyrite have been identified. Stilpnomelane contains increased Mn (up to 2.32 apfu ) and Mg (up to 1.68 apfu ), while being depleted in Ca, K, Ba and Na. Stilpnomelane is considered a retrograde phase, formed by the partial dissolution of spessartine under the lower greenschist facies conditions. The carbonate-silicate bodies of manganese mineralization consist of rhodochrosite, kutnohorite, calcite, rhodonite group minerals, spessartine, tephroite, pyrosmalite-(Mn), magnetite, pyrophanite, clino-suenoite, clino-ferro-suenoite, actinolite, clinochlore, chamosite, caryopilite, greenalite, quartz, alabandite, pyrite, pyrrhotite, galena, sphalerite and chalcopyrite. This manganese assemblage is a result of multistage metamorphism during the Variscan and Alpine tectono-metamorphic evolution, resulting in characteristic mineral assemblages influenced by release or incorporation of Fe-enriched fluids, alteration of silicates and recrystallization of newly generated phases. Polycyclic development is most evident in spessartine crystals, which display chemically distinguishable zones reflecting the multi-stage metamorphic development of manganese mineralization. The presence of significantly Fe-rich tephroite (up to 31 mol.% fayalite), pyrosmalite-(Mn) (up to 2.39 apfu Fe), magnetite, pyrophanite, rhodochrosite and quartz inclusions considered as residual phases in spessartine preserves the primary chemical composition of the later developing manganese ore. This suggests its concurrent forming with nearby magnetite lenses, as well as observed at the other Western Carpathian occurrences. Post-Variscan hydrothermal activity, influenced by suitable host rocks, led to the larger accumulation of sulfides in low-pressure and low-temperature metamorphic manganese occurrences in the Western Carpathians. Spišsko-gemerské rudohorie Mts. Smolník manganese mineralization metacarbonates rhodonite spessartine stilpnomelane Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Introduction The deposits with accumulated presence of metamorphosed manganese mineralization in the Western Carpathians are currently intensively studied at the several localities within the Spišsko-gemerské rudohorie Mountains. They are characteristic by very diverse mineral assemblages, which are at the Čučma, Smolník and Betliar occurrences hosted in silicate-carbonate lenticular bodies bound to the Early Palaeozoic greenschist facies metavolcanosedimentary complexes of Bystrý potok Formation (Gelnica Group). Similarly, metamorphic magnetite-manganese ores were recently discovered and described from the Prakovce – Zimná Voda prospect within the Early Palaeozoic volcanogenic-sedimentary rocks of Drnava Formation (Gelnica Group). These Southern Gemericum occurrences represent important mineral assemblages consisting of approximately 110 different mineral species (Kantor 1953 ; Faryad 1994 ; Peterec & Ďuďa 2003 ; Rojkovič 1999 , 2000 , 2001 ; Števko et al. 2015 , 2023 ; Radvanec & Gonda 2020 ; Myšľan et al. 2023 , 2024a etc.) Furthermore, in the Northern Gemericum in the Rakovec Group manganese metasediments were described from borehole RHV-1 near Rudňany (Spišiak et al. 1989 ; Spišiak & Hovorka 2000 ) and a new occurrence of As-enriched manganese mineralization was recently discovered at the locality Poráč – Diely, featuring a notable mineral assemblage that includes, in addition to silicates and carbonates, Li-pyroxenoids, arsenosilicates and arsenates (Myšľan et al. 2024b ). Exploration and mining at the Southern Gemeric Smolník – Malá Hekerová, sometimes also referred as Bystrý potok manganese deposit has begun in the second half of the 19th century. According to the archive data, during the 1880–1885 period approximately 2 600 t of secondary manganese ores from hypergene zones were extracted out of an estimated volume of 32 000 t. The mining fields were delineated and later grouped to the Attila-Zoltán mining field (Kantor 1953 , 1954 ; Ilavský & Polák 1967 ). A slightly extensive work on manganese mineralization at the studied deposit was published by Rojkovič ( 1999 , 2000 , 2001 ), who described the basic mineral composition of manganese ores with its probable genetic interpretation. This article provides more detailed mineralogical research of the manganese mineralization at the Smolník – Malá Hekerová deposit and supplies significant amount of new data focusing on chemical and structural changes in primary phases embedded in manganese ore and associating metacarbonate bodies. Geological settings and localization Manganese mineralization at the Smolník – Malá Hekerová deposit occurs within the Early Palaeozoic, low-grade metamorphic rocks of the Gemeric Unit (Gemericum), situated in the northeastern region of the Spišsko-gemerské rudohorie Mountains, eastern Slovakia. The Gemeric Unit comprises several stratigraphic sequences: Lower Palaeozoic basement (Gelnica and Rakovec Groups), Upper Palaeozoic complexes (Ochtiná, Dobšiná and Gočaltovo Groups), and a Lower Triassic cover (Kobeliarovo Group) (Bajaník et al. 1983 ). The Lower Paleozoic basement is interpreted to have a riftogenic origin and is associated with the active Gondwana margin (Grecula 1982 ; Putiš et al. 2008 ). These sequences were later penetrated by Permian S-type granites (Uher & Broska 1996 ). The Lower Palaeozoic complexes of the Gelnica Group underwent regional metamorphism during the Variscan and Alpine tectonic events, occurring under the greenschist facies conditions (Faryad 1991 , 1995 ; Vozárová et al. 2014 ). The Gelnica Group represents low-grade Early Palaeozoic metamorphosed formation with polygenetic and polycyclic development retaining megasequences of flyschoid sedimentation characteristics alongside with syngenetic acid (rhyolite-dacite) and minor basic volcanism. The age of Gelnica Group has been firstly established biostratigraphically indicating the Upper Cambrian to the Lower Devonian (Snopková & Snopko 1979 ), later U-Pb SHRIMP dating of zircons extracted from rhyolite metavolcanoclastic rocks defined its age (464–460 Ma) to the uppermost Middle Ordovician (Vozárová et al. 2017 ). This Group is divided into three litostratigraphic units, namely Vlachovo, Bystrý potok and Drnava Formations (Bajaník et al. 1983 ). Lenses with manganese mineralization at the Smolník – Malá Hekerová deposit (Fig. 1 ) are hosted in the metacarbonate bodies of the Bystrý potok Formation, surrounded by graphitic and quartz-muscovitic phyllites and metalydites associated with metavolcanoclastic material (tuffs and tuffites) (Bajaník et al. 1983 ; Vozárová 1993 ). The Smolník – Malá Hekerová manganese deposit is situated approximately 4 km northwestern of the Smolník town (Gelnica district, Košice region), on the southern slopes of the Bystrý potok valley, northern to the Malá Hekerová hill. The manganese locality comprises of multiple surface outcrops mined by small pits and partially or fully collapsed adits with dumps. The manganese mineralization was found in two adits. The northernmost Mangánová adit with lenticular metacarbonate body with associated manganese mineralization reaching thickness of 2–3 m, where body was monitored to the surface with thickness up to 4 m, and second adit with small amounts of manganese ore situated further to the west. Southwest at a distance of approximately 200 m, a third adit (referred to as the Magnetitová adit) was driven in crystalline limestones, which encountered a position of magnetite 0.2–0.3 m thick associated with rhodonite and Fe oxides with a high Mn content (up to 27.73 wt.%; Kantor 1953 ). The main sampling area was localized at the main lower dump with GPS coordinates xx (at altitude x m a. s. l.) and upper dump with GPS coordinates xx (at altitude x m a. s. l.), corresponding to the Manganová adit surroundings. Two samples of associating metacarbonate bodies were collected at the nearby outcrop with GPS coordinates 48°44'51.0"N 20°41'21.8"E (at the altitude x m a. s. l.). Variable representative samples of manganese ores and associated rocks were collected during the 2019–2020 period. Analytical methods The representative samples of metamorphosed manganese mineralization were polished to thin sections and mounts, labelled MH-1 to MH-20 from the dumps and nearby metacarbonate outcrop (MH-2 and MH-3). Quantitative chemical (WDS) analyses of studied minerals were obtained using a JEOL-JXA850F field-emission electron microprobe (EMPA) in wavelength-dispersive spectrometry (WDS) mode (Earth Science Institute, Slovak Academy of Sciences, Banská Bystrica, Slovakia). The following conditions were applied: accelerating voltage 15 kV, measuring current 20 nA (silicates, carbonates) and accelerating voltage 20 kV and measuring current 15 nA (sulfides). The beam diameter ranged from 1 to 10 µm, ZAF correction was used. The following standards and X-ray lines were used: albite (Al Kα , Na Kα ), Ag (Ag Lα ), baryte (S Kα , Ba Lα ), Bi 2 Se 3 (Bi Mα ) CdTe (Cd Lα ), celestine (Sr Lα ), CePO 4 (Ce Lα ), crocoite (Pb Mβ ), Cr 2 O 3 (Cr Kα ), Co (Co Kα ), CuFeS 2 (Cu Kα ), diopside (Si Kα , Mg Kα , Ca Kα ), DyPO 4 (Dy Lβ ), fluorapatite (P Kα ), fluorite (F Kα ), GaAs (As Lα ), gahnite (Zn Kα ), hematite (Fe Kα ), HgTe (Hg Lα ), LaPO 4 (La Lα ), LiNbO 4 (Nb Lα ), LuPO 4 (Lu Lα ), Ni 2 Si (Ni Kα ), NdPO 4 (Nd Lα ), orthoclase (K Kα ), PbSe (Se Lβ ), PbTe (Te Lα ), PrPO 4 (Pr Lβ ), rhodonite (Mn Kα ), rutile (Ti Kα ), Sb 2 S 3 (Sb Lα ), ScVO 4 (V Kα ), SmPO 4 (Sm Lβ ), ThO 2 (Th Mα ), UO 2 (U Mβ ), tugtupite (Cl Kα ), YbPO 4 (Yb Lα ), and YPO 4 (Y Lα ). The detection limit of every element ranged from 0.002–0.030 wt. %. Elements which were analysed quantitatively and are below the detection limit are not listed in the tables. All chemical analyses are listed in Supplementary Table 1. Photographic documentation of relationships between minerals was carried out in the BSE (back scattered electrons) mode. Abbreviations of minerals are defined in Warr ( 2021 ). Powder X-ray diffraction data were collected at room temperature using a Bruker D8 Advance diffractometer equipped with a solid-state LynxEye detector and secondary monochromator producing Cu K α radiation (Department of Mineralogy and Petrology, National Museum, Prague, Czech Republic). The instrument was operating at 40 kV and 40 mA. In order to minimize the background, the powder samples were placed on the surface of a flat silicon wafer. The powder pattern was collected using a Bragg-Brentano geometry in the range 4–70° 2θ, step 0.01° and counting time of 8 s per step (total duration of experiment was ca . 12 hours). The positions and intensities of diffraction effects were found and refined using the Pearson VII profile-shape function of the ZDS program package (Ondruš 1993 ). Unit-cell parameters were refined by the least-squares program of Burnham ( 1962 ). The Raman spectra were obtained using a Thermo Scienctific DXR3xi Raman Imaging microscope at the Natural History Museum (Slovak National Museum) in Bratislava, Slovakia. Two lasers were used during the sample investigation. A 532 nm doubled Nd:YVO 4 DPSS excitation laser, 20 and 50x objective, a 25 µm confocal pinhole, an EMCCD detector with a laser power 10–20 mW for 0.5 s (2 Hz), 15 scans per cycle. Spectral manipulations were performed using the Thermo Fisher Scientific OMNIC c. 9.11 software package. The Raman spectra were collected in the range 30–1800 cm − 1 . Results Textural characteristics of manganese ore and associated metacarbonate bodies The manganese mineralization at the Smolník – Malá Hekerová deposit is hosted within the several meters thick metacarbonate bodies embedded in graphite-muscovitic and quartz-muscovitic phyllites. The metacarbonate is predominantly white to greyish in colour. In areas closely associated with manganese ore, the metacarbonate exhibits a thick black crust along its edges. Internally, it contains stripped zones enriched with light to dark brown spessartine, yellowish titanite and dark greenish stilpnomelane (Fig. 2 a). Close to the contact with manganese ore, the metacarbonate acquires a richer white to slightly pinkish colour, with brown spessartine crystals also visible. The transition from metacarbonate to carbonate-rich manganese mineralization is sharp, marked by a distinct colour change from white to pink (Fig. 2 b). The silicate-carbonate manganese mineralization appears macroscopically light pink due to fine-grained rhodonite, while coarse-grained rhodochrosite causes its darker pink coloration (Fig. 2 c). Similarly, yellow zones and aggregates result from spessartine accumulations, tephroite tends to cause greyish green massive accumulations, while green hues are caused by chlorites and amphiboles, brownish needle-like zones are formed by caryopilite and greenalite. The manganese ore is rich in polymetallic sulfidic mineralization, characterized by accumulations and aggregates up to several cm in size with a metallic lustre, represented by brass-yellow pyrite, pyrrhotite and chalcopyrite, lead-grey galena and red-brown sphalerite (Fig. 2 d). The manganese ore is intersected by an extensive system of veins composed mainly of: (1) rhodonite, carbonate (rhodochrosite, kutnohorite, Mn-rich calcite), quartz and in some area, pyrosmalite-(Mn) and spessartine, (2) rhodochrosite, chlorites, amphiboles, caryopilite and greenalite and (3) polymetallic sulfidic minerals (Fig. 2 c, d). Secondary manganese (hydro)oxides form brown to dark black outer crusts on manganese ore accumulations, they are not part of this study. Mineral composition of the host metacarbonates Metacarbonate bodies associating with carbonate-silicate manganese mineralisation are dominantly composed of calcite (up to 80.9 mol.% CaCO 3 molecule) with increased MnCO 3 molecule (up to 18.8 mol.%; 0.17 apfu Mn) and slightly elevated Fe and Mg (up to 0.01 apfu ) contents (Tab. S1). These metacarbonate bodies locally contain significant accumulations of well-developed spessartine crystals up to 5 mm in size, often grouped to the bigger aggregates. Spessartine crystals are light brown to dark orange, with an abundant magnetite and pyrophanite inclusions. In BSE imaging they show no zoning and along the edges they are slightly corroded by partial dissolution (Fig. 3 a). Chemical composition of garnets shows significant presence of spessartine molecule (70.3–79.9 mol.%) with increased andradite (up to 29.4 mol.%) and minor almandine (up to 4.7 mol.%) molecules (Fig. 4 a). Spessartine contains only elevated amount of Ti (up to 0.04 apfu ) (Tab. S1). Alongside with spessartine, titanite occurs frequently, with macroscopically light-yellow subhedral crystals up to 0.3 mm in size. Titanite is porous and slightly corroded alongside the edges, it also contains inclusions dominantly composed of calcite and less frequently magnetite (Fig. 3 a). Its chemical composition is close to end-member formula with slightly elevated contents of F (up to 0.13 apfu ), Al (up to 0.10 apfu ), Fe 3+ (up to 0.02 apfu ) and Mn (up to 0.01 apfu ). Content of REE elements investigated in titanite is close to the detection limit (less than 0.01 apfu ) (Tab. S1). Stilpnomelane occurs as acicular elongated crystals, often forming dark brown flakes and aggregates. The crystals reach size up to 3 mm and are closely associated with spessartine. They are sometimes found separately in the calcite masses of metacarbonate body, but most frequently they overgrow spessartine crystals along their edges (Fig. 3 a, b). The chemical composition of stilpnomelane is primarily dominated by Fe (3.92–4.19 apfu ), partially substituted by Mn (1.90–2.32 apfu ) and Mg (1.50–1.68 apfu ). Stilpnomelane is largely depleted in alkali and alkaline earth cations, with only minor amount of Ca 2+ (up to 0.33 apfu ), K + (up to 0.15 apfu ), Ba 2+ (up to 0.11 apfu ) and Na + (up to 0.02 apfu ), whereas this octahedral position is dominantly vacant (up to 0.68 apfu ) (Tab. S1). Stilpnomelane was identified by X-ray powder diffraction only as a part of mixture with garnet and probably ilmenite. The observed diffraction maxima of stilpnomelane correspond the best with published data for so-called " manganiferous ferrostilpnomelane " (Table 1 ) from Grythytte, Sweden (Eggleton, Chappell 1978 ). The observed differences in intensities of individual diffraction maxima are due by the by strong preferred orientation effects. Table 1 X-ray powder diffraction data of stilpnomelane from Smolník – Malá Hekerová in comparison with published data for sample from Grythytte, Sweden. this paper Eggleton, Chappell ( 1978 ) d obs I obs d obs I obs 12.216 100.0 12.15 100 7.123 0.8 7.21 10 6.088 2.3 6.07 40 5.525 0.2 5.51 20 4.781 0.4 4.77 30 4.382 0.1 4.38 20 4.054 14.7 4.05 70 3.82 10 3.60 20 3.038 9.1 3.035 60 2.729 1.5 2.735 60 2.646 0.4 2.646 10 2.580 1.0 2.583 100 2.4347 0.2 2.442 30 2.3597 1.0 2.362 80 2.1987 0.6 2.202 40 2.1204 1.9 2.121 60 1.968 30 1.8964 2.7 1.894 30 1.6921 0.6 1.693 40 1.5913 0.2 1.596 80 Fluorapatite occurs rarely as euhedral crystals and grains up to 8 µm in size. Content of the majority elements is close to ideal end-member formula, fluorapatite only shows slightly elevated content of Mn (up to 0.06 apfu), content of ΣREE (Ce 3+ +La 3+ +Nd 3+ +Pr 3+ ) does not exceed 0.01 apfu (Tab. S1). From the polymetallic sulfidic mineralization, only pyrite was identified in metacarbonates associating with all minerals forming euhedral to anhedral crystals and aggregates. Mineral composition of manganese ore Carbonates represent the most common mineral group, which mostly forms carbonate-silicate mineralisation at the studied locality. They predominantly occur as massive fine-grained aggregates, which form matrix, veins and rarely inclusions (Fig. 3 a, b, f, g). Carbonates in the matrix consist of Ca-rich rhodochrosite and kutnohorite. The chemical composition of rhodochrosite shows up to 84.8 mol.% MnCO 3 molecule, with relatively high content of CaCO 3 (up to 28.3 mol.%) and FeCO 3 (5.3 mol.%) molecules. Similarly, in kutnohorite enrichment in Ca leads to an increase in CaCO 3 (up to 68.1 mol.%) and a decrease in MnCO 3 (up to 33.8 mol.%) molecules, along with slightly elevated contents of FeCO 3 (up to 3.3 mol.%) and MgCO 3 (up to 1.8 mol.) molecules (Tab. S1). Vein-type carbonates are the dominant constituent of carbonate-quartz-rhodonite veins, where they mostly occur as rhodochrosite, to a lesser extent as kutnohorite. Rhodochrosite forms up to 0.5 mm thin needle-like crystals grouped to the bigger aggregates. It locally shows elevated content of CaCO 3 molecule (up to 21.9 mol.%), but typically it has the highest content of MnCO 3 molecule observed in this study (up to 94.7 mol. %). It also shows a slightly increased FeCO 3 content (up to 7.24 mol. %) (Tab. S1). The third type of carbonate occurs within the polycrystalline spessartine crystals, separating their inner and other zones (Fig. 5 c-f). This carbonate is classified as Mn-rich calcite, containing up to 78.4 mol.% of CaCO 3 molecule and increased content of MnCO 3 (up to 22.0 mol.%) molecule (Tab. S1). The most common primary silicate minerals identified in the manganese mineralization belong to the rhodonite group, characterized by the general structural formula VII M (5) VI M (1) VI M (2) VI M (3) VI M 4)[Si 5 O 15 ] (Shchipalkina et al. 2019 ). These minerals were identified as rhodonite ( M4 Mn 2+ >0.5) and Fe-rich rhodonite, seamlessly transitioning into ferrorhodonite ( M 4 Fe 2+ >0.5). Rhodonite group minerals form alongside with rhodochrosite main silicate-carbonate mineralization in matrix, where rhodonites occurs as anhedral to subhedral crystals up to 3 mm in size, often grouped to the massive aggregates (Fig. 5 a). Rhodonite was less often identified in the veins overgrowing with rhodochrosite and quartz. In BSE images, no visible zoning within the rhodonite-ferrorhodonite fine-grained masses was observed. The peak positions in both experimental X-ray powder patterns (Table 2 ) agree with data published for ferrorhodonite from type locality (Shchipalkina et al. 2017 ) as well as with those calculated based on Lazy Pulverix program (Yvon et al. 1977 ) from the crystal structure of this mineral (Shchipalkina et al. 2017 ). Differences between observed and calculated diffraction intensity are caused by preferred orientation and other textural effects. The refined unit-cell parameters, compared with published data for members of rhodonite group are given in the Table 3 . Table 2 X-ray powder diffraction data of rhodonite group minerals from Smolník – Malá Hekerová Fe-rich rhodonite ferrorhodonite I obs d obs d calc I obs d obs d calc h k l 18 7.153 7.134 15 7.155 7.141 0 -1 1 25 6.686 6.672 34 6.693 6.679 1 0 0 33 4.774 4.773 24 4.783 4.778 -1 -1 1 5 4.129 4.129 4 4.138 4.133 1 -1 2 2 3.685 3.684 3 3.691 3.687 0 2 0 33 3.569 3.567 38 3.572 3.570 0 -2 2 8 3.415 3.417 6 3.422 3.420 1 -2 1 19 3.344 3.346 11 3.348 3.349 -1 2 0 31 3.337 3.336 42 3.341 3.340 2 0 0 17 3.256 3.256 17 3.261 3.259 -2 0 1 100 3.141 3.140 36 3.144 3.142 -2 1 0 17 3.098 3.097 28 3.101 3.100 0 -2 3 32 3.092 3.092 25 3.096 3.095 -1 -2 2 86 2.980 2.982 100 2.985 2.984 -2 1 1 88 2.973 2.974 99 2.978 2.977 -2 -1 1 49 2.933 2.933 59 2.937 2.935 0 -1 4 10 2.812 2.811 8 2.815 2.814 -2 -1 2 10 2.788 2.788 6 2.792 2.790 -1 -2 3 24 2.766 2.766 22 2.768 2.768 0 2 2 14 2.656 2.656 16 2.658 2.658 1 -1 4 32 2.601 2.601 21 2.604 2.603 2 -2 1 28 2.518 2.518 24 2.521 2.521 0 -3 2 7 2.4582 2.4575 10 2.4610 2.4598 2 1 2 4 2.4303 2.4306 3 2.4324 2.4328 2 0 3 4 2.3870 2.3866 3 2.3885 2.3889 -2 -2 2 9 2.3788 2.3781 7 2.3807 2.3803 0 -3 3 14 2.2322 2.2320 12 2.2341 2.2334 -2 0 4 21 2.2251 2.2246 24 2.2266 2.2263 0 -2 5 6 2.2090 2.2085 7 2.2105 2.2106 -3 0 1 70 2.1801 2.1804 74 2.1827 2.1824 -3 1 0 12 2.1574 2.1579 9 2.1597 2.1600 3 0 1 16 2.1167 2.1165 14 2.1190 2.1181 -1 -2 5 6 2.0962 2.0971 6 2.0986 2.0988 1 3 1 11 2.0685 2.0693 3 2.0710 2.0712 2 -3 2 5 1.9807 1.9805 3 -2 1 15 1.8985 1.8987 6 1.9001 1.9005 -2 -3 3 14 1.8744 1.8747 14 1.8708 1.8709 3 1 2 9 1.8687 1.8692 0 -4 3 8 1.8436 1.8451 9 1.8454 1.8464 -1 -2 6 3 1.8058 1.8059 2 3 1 3 1.7753 1.7749 4 1.7766 1.7765 -1 -4 3 5 1.7481 1.7482 4 1.7491 1.7496 0 -3 6 6 1.7251 1.7245 8 1.7254 1.7255 0 1 6 19 1.6975 1.6971 11 1.6990 1.6986 2 -3 5 40 1.6653 1.6652 45 1.6665 1.6668 -4 0 1 7 1.6492 1.6498 3 1.6508 1.6510 -3 -1 5 8 1.6398 1.6399 5 1.6410 1.6409 1 1 6 7 1.6057 1.6057 3 1.6062 1.6069 -2 4 1 9 1.5910 1.5910 3 1.5921 1.5926 -3 -3 3 8 1.5863 1.5860 3 1.5871 1.5871 -3 3 2 6 1.5152 1.5151 6 1.5160 1.5165 1 -4 6 10 1.4783 1.4786 10 1.4794 1.4800 3 -3 5 22 1.4321 1.4321 16 1.4332 1.4335 4 2 1 9 1.3871 1.3869 6 1.3878 1.3880 -4 -1 5 Table 3 Unit-cell parameters for members of rhodonite group (for triclinic space group P -1). ferrorhodonite Fe-rich rhodonite ferrorhodonite rhodonite vittinkiite this paper this paper Shchipalkina et al. ( 2017 ) Shchipalkina et al. ( 2019 ) Shchipalkina et al. ( 2019 ) a [Å] 6.7079(8) 6.7015(6) 6.6766(5) 6.67–6.70 6.70–6.71 b [Å] 7.6840(14) 7.6771(11) 7.6754(6) 7.62–7.68 7.62–7.64 c [Å] 11.830(2) 11.8227(18) 11.803(1) 11.78–11.84 11.84–11.86 α [ o ] 105.629(11) 105.612(9) 105.501(1) 105.4-105.6 105.6-105.7 β [ o ] 92.302(12) 92.314(9) 92.275(1) 92.4–92.5 92.4 γ [ o ] 93.995(11) 94.001(8) 93.919(1) 93.9–94.0 94.2–94.3 V [Å 3 ] 584.7(2) 583.28(16) 580.44(1) 577–580 579–580 Chemical composition of rhodonite group minerals show M 5 Ca/(Ca + Mn) ratio in the range 0.52–0.95, while positions M 1, M 2 and M 3 are fully occupied by Mn 2+ . Rhodonite from matrix generally tends to be at the position M 4 enriched in Fe 2+ (up to 0.95 apfu ) within the M 4 Mn/(Mn + Fe) ratio in the range 0.03–0.49. On the other side, rhodonite from veins shows enrichment in Mn 2+ (up to 0.88 apfu ) with M 4 Mn/(Mn + Fe) ratio in 0.51–0.78 interval. Rhodonite group minerals from matrix tend to have slightly elevated content of Mg (up to 0.35 apfu ) compared to those from veins (up to 0.01 apfu ) (Tab. S1). Spessartine is another frequent component in manganese carbonate-silicate ore, forming euhedral to anhedral crystals up to 5 mm in size, often grouped to the bigger aggregates. Spessartine aggregates macroscopically appears as light pink to light orange masses, occurring both in the matrix and veins. Garnets identified in the manganese ore can be categorised into three types based on their appearance, chemical composition and location in ore (Fig. 4 a). The first type of spessartine occurs is dominant component of manganese ore identified in matrix. It forms anhedral to subhedral crystals grouped into aggregates (Fig. 5 c, e, g, h). This type contains numerous inclusions, including quartz, magnetite, pyrophanite, pyrosmalite-(Mn), tephroite and rhodochrosite (Fig. 5 d). Its chemical composition is relatively stable, with spessartine molecule ranging from 82.6 to 93.8 mol.%, slightly elevated andradite molecule (up to 17.2 mol. %) and almandine (up to 0.5 mol. %) molecules are also present (Tab. S1). The second type of spessartine occurs in veins, often associated with rhodochrosite and locally with rhodonite. Veins dominated by spessartine aggregates are macroscopically light orange and can reach up to 1.3 cm in thickness. This type has fewer inclusions, mostly formed by rhodochrosite. Its chemical composition significantly differs by reduced, but still dominant, spessartine molecule (64.2–77.9 mol.%) and increased andradite (up to 35.7 mol.%) and almandine (up to 2.1 mol.%) molecules. The third type of spessartine is represented by polycrystalline aggregates composed of central parts zoned along the edges and newly formed rims separated by thin calcite zone (Fig. 3 c-f). In some cases, the central parts or zones are completely absent, leaving only the newly formed rim identifiable (Fig. 3 c). The central parts (Sps1) has the biggest content of spessartine molecule (up to 89.4 mol.%) with slightly elevated andradite (up to 15.8 mol.%) and almandine (up to 0.3 mol.%) molecules. Surrounding the central sps1 zone, the outer Sps2 zone has lowered content of spessartine (up to 73.3 mol.%) and increased andradite (up to 37.2 mol.%) and almandine (up to 0.3 mol.%) molecules. This zone is porous and in BSE imaging can be differentiated by change in colour. The third garnet outer rim zone (Sps3) is separated from the inner two zones by in average 80 µm thick zone of Mn-rich calcite. The Sps3 zone retains the typical garnet growth shape and consists mainly of spessartine (up to 78.1 mol.%) with elevated andradite (up to 32.9 mol.%) and almandine (up to 9.5 mol.%) molecules (Tab. S1). Tephroite is another abundant mineral in the manganese ore, where it occurs in two forms. The first most common type creates elongated, macroscopically reddish-brow crystals up to 2 mm long and 50 µm thick, closely associated with rhodonite and pyrosmalite-(Mn) embedded in rhodochrosite (Fig. 5 b), rhodonite locally overgrows tephroite. This type of tephroite is formed by up to 90.7 mol.% of tephroite molecule (representing up to 1.83 apfu Mn 2+ ), with minor fayalite (up to 8.7 mol.%; 0.18 apfu Fe 2+ ) and forsterite (up to 2.0 mol.%; 0.04 apfu Mg 2+ ) molecules. The second type of tephroite forms up to 15 µm anhedral inclusions in spessartine, associated with pyrosmalite-(Mn), magnetite and pyrophanite (Fig. 5 d). Chemical composition differs by significant increase in fayalite molecule (up to 31 mol.%; 0.75 apfu Fe 2+ ) and decrease in tephroite molecule (up to 79.1 mol.%; 1.58 apfu Mn 2+ ), while forsterite molecule remains similar to the first type of tephroite (up to 2.5 mol.%; up to 0.05 apfu Mg 2+ ) (Fig. 4 b, Tab. S1). Pyrosmalite-(Mn) occurs commonly in three forms. Firstly, it creates accumulations of weakly zoned crystals up to 10 mm in size, macroscopically forming light yellow aggregates in pinkish manganese ore associated mostly with rhodonite, rhodochrosite, tephroite and spessartine (Fig. 5 c). Crystals show weak zoning caused by content changes of Fe and Mn. Chemical composition of this type of pyrosmalite-(Mn) shows the highest amount of Mn (up to 7.50 apfu ) and the lowest content of Fe (1.74 apfu ). The second type is represented by subhedral grains of pyrosmalite-(Mn) forming inclusions in spessartine associated with tephroite, magnetite and pyrophanite (Fig. 5 d). Chemical composition of these inclusions differs by lowered content of Mn (up to 5.76 apfu ) and increased content of Fe (up to 2.39 apfu ). The third type of pyrosmalite-(Mn) occurs in veins and local accumulations with relatively low Mn (up to 4.82–5.81 apfu ) and elevated Fe (up to 2.97 apfu ) contents (Tab. S1). Substitution of Fe vs Mn shows a linear trend with increasing Fe in vein-type pyrosmalite compared to those pyrosmalite-(Mn) from matrix (Fig. 4 c). Amphibole supergroup minerals, with general formula AB 2 C 5 T 8 O 22 W 2 (Hawthorne et al. 2012 ), are at the studied locality represented by clino-suenoite (☐Mn 2 + 2 Mg 5 Si 8 O 22 (OH) 2 ) (Oberti et al. 2018 ), clino-ferro-suenoite (☐Mn 2 + 2 Fe 2 + 5 Si 8 O 22 (OH) 2 ) (Holtstam et al. 2024 ) as well as actinolite (☐Ca 2 Mg 4.5−2.5 Fe 0.5−2.5 )Si 8 O 22 (OH) 2 ). Amphiboles in the manganese ore occur as greenish to dark brown acicular prismatic crystals with a rhombic cross-section, grouped into larger aggregates. These amphiboles can be found in both the matrix and veins, typically measuring approximately 50 µm to 0.5 mm in size, though locally some crystals can reach up to 3 mm in size. BSE imaging reveals significant zoning, where the mostly outer lightest parts are composed of clino-ferro-suenoite and the mostly inner darker zones are formed by clino-suenoite (Fig. 5 e). Actinolite, on the other hand, mostly occurs in the form of well-developed crystals grouped into the aggregates within the veins or local massive accumulation. Actinolite shows only weak zoning and it consistently overgrows with other amphiboles and vein-type rhodochrosite along the crystal edges (Fig. 5 c-f). The chemical composition of clino-suenoite at the crystallochemical position B shows dominant content of Mn 2+ (up to 1.90 apfu ), while position C dominantly occupied by Mg (up to 3.55 apfu ). Similarly, in clino-ferro-suenoite position B is predominantly occupied by Mn (up to 1.96 apfu ) and the position C is dominantly composed of Fe 2+ (up to 3.54 apfu ). In both amphiboles, the B Ca content does not exceed 0.47 apfu . Additionally, a locally increased content of F − (up to 0.38 apfu ) was observed at the position W (Tab. S1). On the other hand, the chemical composition of actinolite is characterized by dominant Mg (up to 4.02 apfu ) at the position B , compared to lower Fe 2+ (up to 1.22 apfu ) and Mn (up to 0.54 apfu ) contents. The position C is primarily composed of Ca (up to 1.88 apfu ) over Mn (up to 0.75 apfu ). Similarly, an increased F − content (up to 0.41 apfu ) was also observed (Tab. S1). Minerals of the kaolinite-serpentine group were identified as caryopilite (Mn 2 + 3 Si 2 O 5 (OH) 4 ) and greenalite (Fe 2+ ,Fe 3+ ) 2−3 Si 2 O 5 (OH) 4 ). Both minerals were mostly observed as phases crystallized along the edges of predominantly rhodonite crystals (Fig. 5 f), to a lesser content on the other silicates, or as fine needle-like felt aggregates forming up to 0.1 mm thick dark brown veins. Caryopilite exhibits an Fe/(Fe + Mn) ratio in the range of 0.24 to 0.29, while greenalite is in the range 0.50 to 0.55 (Fig. 4 d). Both minerals show elevated content of Mg with up to 0.29 apfu in caryopilite and up to 0.52 apfu in greenalite. Caryopilite has a R/Si ratio (R = Mn + Fe + Mg + Al) in the range of 1.23–1.30, whereas greenalite shows a slightly higher range of 1.29–1.42. Furthermore, caryopilite has slightly elevated content of Cl − (up to 0.08 apfu ) (Tab. S1). Greenalite and caryopilite Raman spectra are given in Fig. 6 . The main bands observed (in wavenumbers) for greenalite are 185, 318, 400, 490, 633, 1028 cm − 1 and caryopilite are 190, 399, 487, 641 and 1027 cm − 1 . Minerals of chlorite group occur frequently, they form fibrous crystals up to 30 µm in size grouped to macroscopically bigger dark green acicular aggregates in narrow veins associated with Mn-rich carbonates and quartz. They were also observed associated with rhodochrosite replacing spessartine (Fig. 5 g). In BSE imaging they are slightly zoned. Chemical composition reflects their variability in content of Fe, Mg and Mn. Clinochlore has Mg/(Mg + Fe) ratio in the range 0.51–0.59 with slightly elevated content of Mn (up to 0.30 apfu ), chamosite with Mg/(Mg + Fe) ratio in the range 0.17–0.20 shows significantly increased content of Mn (up to 0.76 apfu ), due to which, in some analyses, pennantite substitution (up to 0.76 apfu Mn) is present more than clinochlore substitution (up to 0.73 apfu Mg) (Tab. S1). Magnetite is the most common accessory mineral in manganese ore. It forms anhedral to subhedral crystals in rhodonite-rhodochrosite matrix, locally magnetite is present in the form of inclusions in spessartine (Fig. 5 d). It was also identified in the nearby Magnetitová adit forming magnetite bodies. Chemical composition is close to the ideal end-member formula with slightly elevated content of Mn (up to 0.05 apfu ) (Tab. S1). Pyrophanite belongs to accessory minerals in manganese ores, where it occurs in the form of inclusions in other minerals, mostly in spessartine or rhodonite. It forms elongated subhedral crystals up to 30 µm in size. Pyrophanite was rarely found in one sample in the form of well-developed and strongly zoned crystals up to 0.2 mm in size associated with spessartine, rhodonite, rhodochrosite and pyrosmalite-(Mn) (Fig. 5 h). Zonality is caused by relatively strong substitution of Mn and Fe, where pyrophanite molecule occurs within the range 67.45–93.82 mol.% (0.65–0.93 apfu Mn) compensated with ilmenite molecule in the range 6.78–32.55 mol.% (0.06–0.32 apfu Fe) (Tab. S1). Alabandite is rare mineral identified in rhodochrosite assemblages in carbonate-silicate matrix, where it forms anhedral aggregates up to 0.5 mm in size. Macroscopically alabandite is black colour with metallic lustre. It contains a large amount of pyrrhotite inclusions up to 10 µm in size (Fig. 7 a). Chemical composition is characteristic with composition close to the ideal end-member formula with Mn (0.99–1.02 apfu ) and S (0.99–1.01 apfu ). Alabandite contains up to 5.9 wt.% of FeO (up to 0.09 apfu Fe, respectively). Polymetallic sulfidic mineralisation in carbonate-silicate manganese ore is relatively common and is represented by pyrite, pyrrhotite, chalcopyrite, galena and sphalerite (Fig. 7 b). Minerals occur in the form of isolated crystals and polyphase aggregates embedded in the ore matrix and veins. Single and well-terminated crystals reach size up to 1 cm, with even bigger aggregates. No significant zoning in BSE was observed, also reflecting its homogenous chemical composition (Fig. 7 c, d). Chemical composition of all sulfides is close to the end-member formula with Ni, Co, Bi, Hg or Sb components reaching less than 0.01 apfu . Only in sphalerite elevated content of Mn (up to 0.02 apfu ) was observed (Tab. S1). Discussion Origin of metacarbonate bodies and manganese mineralization Metacarbonates originally formed as organodetritic allodapic limestones, that were part of hemipellagic sediments (Bajaník et al. 1983 ; Kováčik 2004 ) and were later metamorphosed and deformed during the Variscan and Alpine development of the Spišsko-gemerské rudohorie Mts. (Grecula et al. 1995 ; Vozárová et al. 2014 , 2017 ). Their lamination results from differences in composition, structure, and mineral grain size, as well as metamorphic deformation (Kobulský et al. 2006 ; Grecula et al. 2011 ), similar to the features observed in the studied metacarbonates associating with manganese ore (Fig. 2 a). The mineral composition of metacarbonates reflects their original pre-metamorphic composition, which includes significant content of pelitic and volcanoclastic material. This composition was subsequently modified by metamorphic and, in some cases, metasomatic processes (Grecula et al. 2011 ). Metacarbonates from Gelnica Group often contain manganese ore lenses, locally associated with magnetite bodies. Rojkovič ( 1999 , 2000 , 2001 ) proposed that manganese migrated from the deep, oxygen-poor regions of the ocean to shallower, oxygen-rich waters, where it formed basic manganese oxides and hydroxides, serving as a primary precursor to more complex carbonates and silicates. Kantor ( 1954 ) and Grecula et al. ( 1995 ) suggested that mineralization resulted from volcano-sedimentary processes linked to basaltic volcanic activity. These processes, accompanied by hydrothermal vent exhalations produced Fe, Mn, SiO₂, and H₂S, indicating a significant influence of submarine volcanic and hydrothermal fluids (Ilavský 1957 ; Grecula et al. 1995 ) or a volcanogenic-exhalative origin (Mücke et al. 2001 ; Mücke 2005 ). Additionally, diagenetic processes involving organic material (metamorphosed equivalents identified in associating lydites and graphite-muscovitic phyllites) contributed to manganese precipitation (Rojkovič 1999 , 2000 , 2001 ). The average calculated temperature of clinochlore crystallization in association with muscovite in metacarbonates acquired by two chlorite geothormometers reaches the interval 357–362 ± 6°C (Myšľan & Ružička, 2022 ). Sassi & Vozárová ( 1987 ) and Mazzoli & Vozárová ( 1989 ) estimated greenschist facies conditions in the range of 300–440°C at the 3–5 kbar. Associated metacarbonates and manganese mineralization underwent metamorphism at 375–420°C under 3.5 kbar (Faryad 1991 , 1994 ; Rojkovič 1999 ), as calculated for the Čučma-Čierna baňa manganese deposit, suggesting similar conditions at the studied locality. Mineral composition of metacarbonate bodies In the metacarbonates of the Gelnica Group, except of calcite, mostly chlorite group minerals (chamosite and clinochlore), muscovite, feldspars, quartz and accessory fluorapatite and rutile were identified (Myšľan & Ružička, 2022 ). Only metacarbonates closely associated with manganese ores at the Čučma deposit contain diopside and grossular (Ružička et al. 2020 ). The elevated manganese content in these metacarbonates suggests deeper-water sedimentation conditions with subsequent manganese incorporation, genetically linked to the oceanic environment (Vozárová & Ivanička 1993 ). At the studied locality, content of MnCO 3 molecule in metacarbonate bodies is elevated (up to 29.7 mol.%), suggesting close relation of manganese and carbonate production. Metacarbonates at the studied deposit contain an accumulations of spessartine, titanite, stilpnomelane and locally hydrothermal pyrite. In titanite, the Ti content is slightly decreased (0.89–0.96 apfu ) due to the substitution (Al,Fe 3+ ) + (OH,F) − ↔ Ti 4+ + O 2− , as evidenced by the small increase in F content (up to 1.3 wt.%; 0.13 apfu ). Low compositional range of Al + Fe 3+ (0.05–0.12 apfu ) and F (0.05–0.13 apfu ) (Tab. S1) is typical for low-pT titanites rather than those high-pT (F > 0.50 apfu ) (Enami et al. 1993 ). Spessartine in metacarbonate closely associated with manganese ore was probably formed through decarbonation and dehydration reactions based on reactions with minerals embedded in precursor Mn-rich carbonates, quartz and clay minerals. Pure spessartine formation begins during the low-pressure and temperature prograde metamorphism at the as low as ~ 300ºC (Theye et al. 1996 ). Stilpnomelane is restricted mineral of the mostly low grade metamorphic conditions (Miyano 1982 ; Feininger 1984 ; Wang et al. 2023 , etc.) in various types of rocks forming during both prograde and retrograde metamorphism, only rarely it occurs in blueschist facies (Potel et al. 2006 ). Li et al. ( 2000 ) suggested, that stilpnomelane formed via replacing chlorite and preserving the primary grain orientation during the prograde metamorphism, but mostly it can form as newly crystallized crystals from water-rich solutions replacing earlier minerals such as garnets or micas and filling veins during the retrograde metamorphism (Kryza et al. 1990 ). The occurrence of stilpnomelane was reported from Čučma – Čierna baňa manganese deposit associated with kutnohorite-ankerite-quartz veins (Faryad 1994 ; Peterec & Ďuďa 2003 ). Stilpnomelane in the studied metacarbonates based on mutual relationship with spessartine appears to be a younger mineral formed by partial dissolution and replacement of spessartine generated as a recrystallization product along the consumed spessartine outer cores (Fig. 3 b). These textures strongly indicate lower greenschist facies conditions, aligning with the previous calculated results. Stilpnomelane contains significant Mn (up to 2.32 apfu ), suggesting substitution with its Mn-analogue franklinphilite K 4 Mn 48 (Si,Al) 72 (O,OH) 216 ·6H 2 O) (Dunn et al. 1992 ), and Mg (up to 1.68 apfu ), indicating a further solid solution with its Mg-analogue lennilenapeite (K 6 − 7 Mg 48 (Si,Al) 72 (O,OH) 216 ·16H 2 O (Dunn et al. 1984 ), reflecting the extensive compositional variations within these isostructural stilpnomelane group phases. Total alkali content in studied mineral remains low (< 0.5 apfu; Tab. S1), likely due to limited supply of K and Na from the surrounding environment. The deficit is therefore partially balanced by a relatively increased content of Ca, influenced by an abundant presence of Mn-rich calcite and spessartine in the host rocks. Mineral composition and multistage development of manganese mineralization The formation of manganese mineralization at the studied locality was probably caused by the transport of primary manganese oxides in higher oxidation states (Mn 3+ /Mn 4+ ) to a shallower-water sedimentary environment rich in organic matter. These conditions created anaerobic, CO 2 -rich and reduced conditions that led the crystallization of Mn 2+ carbonates, primarily rhodochrosite. (Brusnitsyn 2007 ; Johnson et al. 2016 ). Further formation of Mn-rich silicates was influenced by quartz- and clay-rich protolith providing Si, Al, Fe, Mg and other components, necessary for crystallization of silicates produced by continuous increase in metamorphic conditions during the prograde Variscan metamorphic event. Rhodonite remains stable under low-pressure and low-temperature conditions, transformation to a higher pressure/temperature pyroxmangite-type structure was experimentally calculated at 300 MPa pressure and temperatures around 350–400ºC (Maresch & Mottana 1976 ). Additionally, the incorporation of Ca stabilizes the rhodonite-type structure, while Fe 2+ and Mg 2+ further influences stability field towards pyroxmangite-type structure (Jiménez-Milán & Velilla 1998). Based on PXRD data (Table 1 ) and the Ca, Mg and Fe 2+ contents (Tab. S1), along with the suitable metamorphic conditions, a rhodonite-type structure is preserved in the studied rhodonite group minerals. Rhodonite group minerals have increased content of FeO (5.7–10.5 wt.%; Tab. S1), what causes Fe as dominant cation at the position M 4, leaning to the ferrorhodonite composition (Shchipalkina et al. 2019 ). Increased content of FeO (up to 7.1 wt.%) in rhodonites was as well observed by Rojkovič ( 2000 ). Similarly, tephroite forms in the greenschist facies conditions below 420ºC at low X CO2 (< 0.2) (Peters et al. 1973 ) at the expense of rhodochrosite and quartz assemblages (Mohapatra & Nayak 2003). Slightly increased fayalite molecule (8.7 mol.%) is also observed associating with Fe-rich rhodonite, however, inclusions in spessartine contain tephroite with significantly increased fayalite molecule (up to 31 mol.%) (Tab. S1). The absence of rhodonite inclusions in spessartine might be explained due to the absence of pyroxenoids in former association, consequently incorporating Fe in tephroite in the Fe-enriched system in the protolith environment. The presence of magnetite, Fe-rich rhodonite and tephroite permits the greater Fe entry into the coexisting spessartine (up to 17.2 mol. % Adr). Spessartine forms during the early low-pressure stages of prograde metamorphism, with stability field at approximately 300ºC (Theye et al. 1996 ). Spessartine incorporations consisting of quartz, magnetite, pyrophanite, pyrosmalite-(Mn), tephroite and rhodochrosite might represent a residual phases (Nyame 2001 ) of pre-Alpine manganese assemblages. The high content of Fe in these minerals indicates the simultaneous formation of manganese mineralization and nearby magnetite lens and further supports similar characteristics observed in the formation of magnetite lenses associated with manganese ore at the Prakovce – Zimná Voda occurrence (Myšľan et al. 2024a ) and the abundant magnetite impregnations found in the oldest Mn assemblage at the Beltiar – Július locality (Myšľan et al. 2023 ). Pyrosmalite-(Mn) was generated via hydration and chlorination processes of the Mn-rich silicates (Stillwell & McAndrew 1957 ). Further development of carbonate-silicate manganese mineralization at the Smolník - Malá Hekerová deposit was during the Alpine stage of metamorphism significantly influenced by tectono-metamorphic deformation forming the cracks and fissures and subsequent recrystallization and precipitation of newly formed mineral assemblages incorporated mostly in the form of veins. Veins are dominantly filled with quartz, slightly Fe-enriched rhodochrosite, kutnohorite and Fe-poor rhodonite. Rhodonite is often overgrown by caryopilite (Fig. 5 f) or greenalite, which is formed as a retrograde product during the greenschist metamorphism by alteration of anhydrous Si-rich phases (Abrecht 1989 ). These phyllosilicates also occur in veins. Slightly increased content of Cl − in caryopilite (up to 0.08 apfu ) suggests its syngenetical formation with a vein-type pyrosmalite-(Mn) enriched in Fe (up to 2.97 apfu ) during the infiltration or remobilization of H 2 O and Cl-rich fluids. Clinochlore-chamosite chlorites with increased pennantite molecule (up to 0.76 apfu ) (Tab. S1) occur in veins, locally partially replacing spessartine (Fig. 5 g), suggesting their retrograde formation. Changes in Fe content in minerals reflects its mobility during the Alpine metamorphic development, where Fe was released from the primary phases and subsequently incorporated to the newly generated or recrystallized minerals. Amphiboles were observed mostly in the veins, locally forming a massive aggregates with strong zoning. The stability of Mg-Fe-Mn amphiboles depends on the Mn/(Mn + Mg) ratio. The lower stability limit of clino-suenoite was established at the temperature around 400ºC and 200 MPa pressure, which might be influenced by iron content reducing its stability limits (Melcher 1995 ). Association of present amphiboles is not common, they were identified only at a few localities, such as the Pb-Zn skarn deposits in Madan, Bulgaria, where they formed through hydrothermal alteration and replacement of early Mn-rich pyroxenes (Vassileva & Bonev 2001 ). Studied clino-suenoite and clino-ferro-suenoite appear to replace actinolite (Fig. 5 e) while maintaining its original shape. The replacement involves cation exchange, with removal of Ca 2+ and incorporation of Mn 2+ gradually replaced by Mg 2+ and Fe 2+ . These processes depend on metamorphic pT conditions as well as low to moderate oxygen fugacity ( f O 2 ), which stabilizes Mn 2+ within the silicate structure (Brusnitsyn 2007 ; Kanungo et al. 2014 ). The formation of a clino-ferro-suenoite rim around clino-suenoite aligns with increased Fe mobility and its incorporation into later minerals during the Alpine metamorphic stage. The compositional and textural changes in manganese ore during the metamorphic evolution can be best observed at spessartine garnets (Fig. 3 c-f). The central part of garnets (Sps1) consists of relatively stable and homogenous mass, interrupted only with small cracks. The formation of this garnet is consistent with the processes taking place during the prograde stage of metamorphism discussed above. The outer part of garnet (Sps2) shows increased porosity and a change in chemical composition, with decreased Mn (up to 73.3 mol.% Sps2) and increased Fe (up to 37.2 mol.% Adr; up to 0.3 mol.% Alm) contents compared to sps1. This change is likely caused by the partial dissolution of garnet outer parts accompanied by release of Mn and/or incorporation of Fe-rich fluids during the retrograde phase along the garnet outer boundary. The third stage is characteristic by enrichment of CO 2 and Ca in metamorphic environment, resulting in crystallization of thin calcite zone, separating the third spessartine generation (Sps3). This spessartine forms homogenous rims around pre-existing minerals, enriched in Fe (up to 32.9 mol.% Adr; up to 9.5 mol. Alm) and decreased in Mn (up to 78.1 mol.% Sps3). The Sps1 and Sps2 garnets are locally completely dissolved, resulting in elements release to the system with concurrent incorporation of Fe-rich fluids generating the zones of Sps3 garnet. Significance of fluid infiltration during the formation of new generation of garnets has been proved by various authors (Konrade-Smolke et al. 2007; Faryad et al. 2010 ). Rarely alabandite occurs associated with rhodochrosite, it has been suggested to be temperature dependant phase, manifested by an increase in Fe content (Skinner & Luce 1971 ), and FeS activity (Fukuoka 1981 ). Alabandite remains stable within the stability field of iron, pyrrhotite and pyrite under consistently reduced conditions (Cabral et al. 2019 ), stability field expands with increasing temperature (Holland 1959 ). However, increased content of Fe in alabandite cannot be clearly ruled out to be caused by pyrrhotite inclusions (Fig. 7 a). Sulfidic mineralization bound to the manganese carbonate-silicate ore at the Smolník – Malá Hekerová deposit likely formed from hydrothermal fluids linked to Alpine tectono-metamorphic evolution. Their presence in cavities and veins suggests its late formation. Unlike other deposits in the Spišsko-gemerské rudohorie Mts., there is no significant enrichment in Co or Ni, however it displays one of the biggest accumulation of these phases in the area of study interest. High incorporation of these phases to the manganese ore was observed, though Mn enrichment in sulfides remains minimal (up to 0.02 apfu ; Tab. S1). This high sulfides concentration may be attributed to the surrounding lithology, such as metalydites and graphitic phyllites, which provided the necessary sources of sulphur and other elements during the Alpine metamorphic stage. The last stage of manganese ore evolution is characterised by formation of supergene zone, which is not part of this study, however Rojkovič ( 2000 , 2001 ) identified pyrolusite, todorokite, cryptomelane, goethite and limonite as oxidation products of primary mineral association. Conclusions A polygenetic mineral assemblage of metamorphosed carbonate-silicate manganese ore at the Smolník – Malá Hekerová deposit is closely related with metacarbonate bodies hosted in lydites, quartz-muscovitic and graphite-muscovitivic phyllites of metavolcano-sedimentary sequences of the Bystrý potok Formation (Gelnica Group). Mineralization in associating metacarbonate bodies shows huge variety of phases, identified as calcite (locally enriched in Mn), spessartine, stilpnomelane, titanite, fluorapatite and pyrite, suggesting to a certain content manganese incorporation to the precursor carbonate sedimentary environment. Spessartine and titanite are formed during the prograde stage of Variscan metamorphic development at the temperatures as low as ~ 300ºC. Stilpnomelane was formed through mineral replacement of spessartine, aligning with lower greenschist facies conditions. Stilpnomelane exhibits compositional variation due to Mn and Mg substitution and increased Ca component in mineral structure, reflecting the chemical composition of host rocks. The manganese carbonate-silicate ore contains Variscan and Alpine mineral assemblages consisting of rhodochrosite, kutnohorite, rhodonite-ferrorhodonite series, spessartine, tephroite, pyrosmalite-(Mn), magnetite, pyrophanite, clino-suenoite, clino-ferro-suenoite, actinolite, caryopilite, greenalite, chamosite, clinochlore, quartz, alabandite and sulfidic mineralization identified as pyrite, pyrrhotite, galena, sphalerite and chalcopyrite. The first generated mineral assemblage developed during the prograde metamorphism in greenschist facies condition, later processes led to the deformation and vein formation with subsequent filling of younger generation of mineral assemblages, alongside with infiltration of Fe-rich fluids, alteration of Si-rich phases, recrystallization and retrograde metamorphism. Compositional and textural changes in manganese ore are most evident in spessartine garnets, where the core (Sps1) remains stable with high Mn content (up to 89.4 mol.% Sps), while the outer zone (Sps2) shows increased porosity, decreased Mn (73.3 mol.% Sps) and elevated Fe (37.2 mol.% Adr) due to fluid interaction during retrograde metamorphism. A third spessartine generation (Sps3) formed as Fe-rich fluids infiltrated, leading to crystallization of new spessartine zone. Sulfidic mineralization in manganese ore likely resulted from hydrothermal fluids during Alpine tectono-metamorphic evolution, with high sulfide concentrations in manganese ore. Declarations Author Contribution Conceptualization: [P.M., M.Š.], Methodology: [P.M., J.S., T.M.], Figures: [P.M., J.S.], Writing - original draft preparation: [P.M., M.Š., J.S., P.R.]. Acknowledgement: The authors are thankful to handling editor XY as well as reviewers XY1 and XY2 and for their suggestions. We also want to thank B. 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Mineral Mag 85:291–320 Yvon K, Jeitschko W, Parthé E (1977) Lazy Pulverix, a computer program for calculation X-ray and neutron diffraction powder patterns. J Appl Cryst 10:73–74 Additional Declarations No competing interests reported. Supplementary Files Tab.S1Supplementarychemicalanalyses.xlsx Cite Share Download PDF Status: Published Journal Publication published 03 Jun, 2025 Read the published version in Mineralogy and Petrology → Version 1 posted Editorial decision: Revision requested 16 Mar, 2025 Reviews received at journal 06 Mar, 2025 Reviewers agreed at journal 02 Mar, 2025 Reviewers invited by journal 27 Feb, 2025 Editor assigned by journal 24 Feb, 2025 Submission checks completed at journal 24 Feb, 2025 First submitted to journal 20 Feb, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6072303","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":420231297,"identity":"237e63e2-7993-429c-9610-fab3150160eb","order_by":0,"name":"PAVOL MYŠĽAN","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA8UlEQVRIiWNgGAWjYLCCByCCHYg/ALEBEDM2ENKSACKYgSpnkKyFmYcYLebsZwwfJDBsS5zfzPzssc0fu8Tt7AeYP87Ao8WyJ8fYIIHhduKGw2zmxrltyYk7exLYJDfg0WJwIC1NAqyFmcFMOreB2djgQAIb4wN8Ws4/g2iZ38z+TdriT72xwfkHzB/xarmRfAyspeEwj5k0A9thOYMbCQx4HWY54/FhgwSD28YbDvOUSfa2HZeznPGwTRKf9835ExsffKi4LTu/vX2bxI8/1Tzm/MmHP/bgcxiUdGxAiBGISAMobY9X1SgYBaNgFIxsAADCrk/BBitbOgAAAABJRU5ErkJggg==","orcid":"","institution":"Slovak Academy of Sciences","correspondingAuthor":true,"prefix":"","firstName":"PAVOL","middleName":"","lastName":"MYŠĽAN","suffix":""},{"id":420231298,"identity":"d293338f-6528-4c0b-b849-de1f96e65280","order_by":1,"name":"MARTIN ŠTEVKO","email":"","orcid":"","institution":"Slovak Academy of Sciences","correspondingAuthor":false,"prefix":"","firstName":"MARTIN","middleName":"","lastName":"ŠTEVKO","suffix":""},{"id":420231299,"identity":"ffcfcc1a-a33e-422a-9135-39f895903bdd","order_by":2,"name":"JIŘÍ SEJKORA","email":"","orcid":"","institution":"National Museum","correspondingAuthor":false,"prefix":"","firstName":"JIŘÍ","middleName":"","lastName":"SEJKORA","suffix":""},{"id":420231300,"identity":"1faf724d-badf-4668-8251-098c447db1ee","order_by":3,"name":"PETER RUŽIČKA","email":"","orcid":"","institution":"Comenius University in Bratislava","correspondingAuthor":false,"prefix":"","firstName":"PETER","middleName":"","lastName":"RUŽIČKA","suffix":""},{"id":420231301,"identity":"36ae33a4-64f8-4628-9d1e-b85a386d5842","order_by":4,"name":"TOMÁŠ MIKUŠ","email":"","orcid":"","institution":"Slovak Academy of Sciences","correspondingAuthor":false,"prefix":"","firstName":"TOMÁŠ","middleName":"","lastName":"MIKUŠ","suffix":""}],"badges":[],"createdAt":"2025-02-20 13:23:16","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6072303/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6072303/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s00710-025-00922-4","type":"published","date":"2025-06-03T15:57:38+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":77213445,"identity":"ecbd9491-c1e6-4c76-af9f-596440f47fa7","added_by":"auto","created_at":"2025-02-26 09:15:41","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":539856,"visible":true,"origin":"","legend":"\u003cp\u003eGeological map of the studied area with marked location of Smolník – Malá Hekerová manganese occurrence (modified after Bajaník et al. 1983).\u003c/p\u003e","description":"","filename":"floatimage1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6072303/v1/f9588eae25f6b560a2e30ccc.jpeg"},{"id":77213444,"identity":"51e810e6-ae1e-4bea-945b-eaab04512615","added_by":"auto","created_at":"2025-02-26 09:15:41","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":485328,"visible":true,"origin":"","legend":"\u003cp\u003eRepresentative samples of manganese mineralisation at the locality Smolník – Malá Hekerová;\u003cstrong\u003e a: \u003c/strong\u003ecrystalline limestones with actinolite (green), spessartine and stilpnomelane (light brown); \u003cstrong\u003eb:\u003c/strong\u003e contact of crystalline limestone with manganese ore dominantly composed of rhodochrosite (pink); \u003cstrong\u003ec:\u003c/strong\u003e rhodonite-rhodochrosite sample with extensive system of quartz and rhodochrosite-spessartine veins and spessartine accumulations (orange); \u003cstrong\u003ed:\u003c/strong\u003e Rhodonite ore intensively mineralised with sulfidic phases (mostly pyrite, pyrrhotite, galena, sphalerite)\u003c/p\u003e","description":"","filename":"floatimage2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6072303/v1/9a6f036a6dcc9f46203c024f.jpeg"},{"id":77214223,"identity":"29f6a917-7ff5-4445-bc13-fbcc77920ee3","added_by":"auto","created_at":"2025-02-26 09:23:42","extension":"jpeg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":1156339,"visible":true,"origin":"","legend":"\u003cp\u003eBSE images of minerals from the associated metacarbonate bodies and manganese mineralisation at the Smolník – Malá Hekerová deposit; \u003cstrong\u003ea:\u003c/strong\u003e spessartine crystals associated with titanite with outher cores overgrown with stilpnomelane, younger sulfidic mineralisation formed by pyrite in metacarbonate; \u003cstrong\u003eb:\u003c/strong\u003e detail of stilpnomelane associated with spessartine in metacarbonate; \u003cstrong\u003ec:\u003c/strong\u003e the older spessartine1 and 2 overgrown with younger Mn-rich calcite and spsessartine3; \u003cstrong\u003ed:\u003c/strong\u003e general overview of zoned garnet crystal with spessartine1 core and spessartine2 rim overgrown with younger Mn-rich calcite and spessartine3 garnet in rhodonite- and amphibole-rich matrix; \u003cstrong\u003ee:\u003c/strong\u003e detailed view on spessartine3 and Mn-rich calcite zone; \u003cstrong\u003ef:\u003c/strong\u003e Nearly completely overgrown spessartine1 and 2 by newly formed Mn-calcite and spessartine3 garnet in amphibole- and pyrosmalite-(Mn)-rich part of manganese ore\u003c/p\u003e","description":"","filename":"floatimage3.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6072303/v1/ce0b6525b46bcf6e07d9d695.jpeg"},{"id":77213446,"identity":"ccddf54a-89c5-4584-89d7-4ff7faf19ac0","added_by":"auto","created_at":"2025-02-26 09:15:41","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":184586,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ea: \u003c/strong\u003eClassification diagram for spessartine; \u003cstrong\u003eb:\u003c/strong\u003e Substitution diagram Fe vs. Mn (\u003cem\u003eapfu\u003c/em\u003e) in tephroite; \u003cstrong\u003ec:\u003c/strong\u003e Substitution diagram Fe vs. Mn (\u003cem\u003eapfu\u003c/em\u003e) in pyrosmalite-(Mn); \u003cstrong\u003ed:\u003c/strong\u003e Substitution diagram Mn vs Fe (\u003cem\u003eapfu\u003c/em\u003e) in caryopilite-greenalite at the Smolník – Malá Hekerová deposit\u003c/p\u003e","description":"","filename":"floatimage4.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6072303/v1/45a74e5d49493407453d78cd.jpeg"},{"id":77213447,"identity":"05f261ee-168a-4bf1-b48b-6f9e1981e8ca","added_by":"auto","created_at":"2025-02-26 09:15:41","extension":"jpeg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":948789,"visible":true,"origin":"","legend":"\u003cp\u003eBSE images of main and accessory minerals from manganese mineralisation at the Smolník – Malá Hekerová deposit; \u003cstrong\u003ea:\u003c/strong\u003ea general overview of manganese ore forming rhodonite-rhodochrosite matrix with quartz-carbonate veins; \u003cstrong\u003eb:\u003c/strong\u003e tephroite acicular crystals associated with rhodonite and rhodochrosite; \u003cstrong\u003ec:\u003c/strong\u003e slightly zoned pyrosmalite-(Mn) accumulation in rhodonite-spessartine-rhodochrosite matrix; \u003cstrong\u003ed:\u003c/strong\u003e quartz, pyrosmalite-(Mn), tephroite, pyrophanite and magnetite inclusions in spessartine; \u003cstrong\u003ee:\u003c/strong\u003e zoned aggregates of clino-suenoite and clino-ferro-suenoite in manganese ore; \u003cstrong\u003ef:\u003c/strong\u003e recrystallization of rhodonite forming caryopilite rim; \u003cstrong\u003eg:\u003c/strong\u003echlorite group minerals with rhodochrosite overgrowing spessartine; \u003cstrong\u003eh:\u003c/strong\u003e strongly zoned pyrophanite crystals in manganese ore.\u003c/p\u003e","description":"","filename":"floatimage5.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6072303/v1/7c22231b3958b482c544eabe.jpeg"},{"id":77213451,"identity":"848be14d-1331-454c-b742-316e71a82b69","added_by":"auto","created_at":"2025-02-26 09:15:42","extension":"jpeg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":141219,"visible":true,"origin":"","legend":"\u003cp\u003eRaman spectra of \u003cstrong\u003ea:\u003c/strong\u003e greenalite and \u003cstrong\u003eb:\u003c/strong\u003e caryopilite from Smolník – Malá Hekerová deposit in the range 100–1400 cm\u003csup\u003e-1\u003c/sup\u003e\u003c/p\u003e","description":"","filename":"floatimage6.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6072303/v1/a533913e1a7eb8637bf191d2.jpeg"},{"id":77214216,"identity":"5e8f859e-196f-4f01-a6f5-07a2008cc979","added_by":"auto","created_at":"2025-02-26 09:23:42","extension":"jpeg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":585408,"visible":true,"origin":"","legend":"\u003cp\u003eBSE images of sulfidic minerals from manganese mineralisation at the Smolník – Malá Hekerová deposit\u003cstrong\u003e a:\u003c/strong\u003e alabandite aggregate with pyrrhotite inclusions in rhodochrosite;\u003cstrong\u003e b:\u003c/strong\u003e an overview of sulfidic minerals accumulation in carbonate-silicate manganese ore;\u003cstrong\u003e c:\u003c/strong\u003e pyrrhotite overgrowing chalcopyrite in rhodochrosite; \u003cstrong\u003ed:\u003c/strong\u003efine-grained impregnations of sphalerite and galena assemblage in rhodochrosite.\u003c/p\u003e","description":"","filename":"floatimage7.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6072303/v1/8a9589a5e5023744ebf5014f.jpeg"},{"id":84243144,"identity":"dd175b00-ad60-40a4-ba77-b92019733ebf","added_by":"auto","created_at":"2025-06-09 16:12:37","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":5482489,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6072303/v1/4c99d024-ce22-4973-8eff-9b9a1c68125a.pdf"},{"id":77215390,"identity":"6203e22b-5531-4d54-9bd7-e3ef16a6f5b0","added_by":"auto","created_at":"2025-02-26 09:31:42","extension":"xlsx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":202296,"visible":true,"origin":"","legend":"","description":"","filename":"Tab.S1Supplementarychemicalanalyses.xlsx","url":"https://assets-eu.researchsquare.com/files/rs-6072303/v1/1eb72e9f6ce263c4168f0d14.xlsx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Metamorphic manganese mineralization bound to the metacarbonate lenses at the Smolník – Malá Hekerová deposit in the Spišsko-gemerské rudohorie Mts., Western Carpathians (Slovakia)","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe deposits with accumulated presence of metamorphosed manganese mineralization in the Western Carpathians are currently intensively studied at the several localities within the Spišsko-gemersk\u0026eacute; rudohorie Mountains. They are characteristic by very diverse mineral assemblages, which are at the Čučma, Smoln\u0026iacute;k and Betliar occurrences hosted in silicate-carbonate lenticular bodies bound to the Early Palaeozoic greenschist facies metavolcanosedimentary complexes of Bystr\u0026yacute; potok Formation (Gelnica Group). Similarly, metamorphic magnetite-manganese ores were recently discovered and described from the Prakovce \u0026ndash; Zimn\u0026aacute; Voda prospect within the Early Palaeozoic volcanogenic-sedimentary rocks of Drnava Formation (Gelnica Group). These Southern Gemericum occurrences represent important mineral assemblages consisting of approximately 110 different mineral species (Kantor \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e1953\u003c/span\u003e; Faryad \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e1994\u003c/span\u003e; Peterec \u0026amp; Ďuďa \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2003\u003c/span\u003e; Rojkovič \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e1999\u003c/span\u003e, \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2000\u003c/span\u003e, \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2001\u003c/span\u003e; Števko et al. \u003cspan citationid=\"CR65\" class=\"CitationRef\"\u003e2015\u003c/span\u003e, \u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Radvanec \u0026amp; Gonda \u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Myšľan et al. \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2023\u003c/span\u003e, \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2024a\u003c/span\u003e etc.) Furthermore, in the Northern Gemericum in the Rakovec Group manganese metasediments were described from borehole RHV-1 near Rudňany (Spišiak et al. \u003cspan citationid=\"CR62\" class=\"CitationRef\"\u003e1989\u003c/span\u003e; Spišiak \u0026amp; Hovorka \u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e2000\u003c/span\u003e) and a new occurrence of As-enriched manganese mineralization was recently discovered at the locality Por\u0026aacute;č \u0026ndash; Diely, featuring a notable mineral assemblage that includes, in addition to silicates and carbonates, Li-pyroxenoids, arsenosilicates and arsenates (Myšľan et al. \u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e2024b\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eExploration and mining at the Southern Gemeric Smoln\u0026iacute;k \u0026ndash; Mal\u0026aacute; Hekerov\u0026aacute;, sometimes also referred as Bystr\u0026yacute; potok manganese deposit has begun in the second half of the 19th century. According to the archive data, during the 1880\u0026ndash;1885 period approximately 2 600 t of secondary manganese ores from hypergene zones were extracted out of an estimated volume of 32 000 t. The mining fields were delineated and later grouped to the Attila-Zolt\u0026aacute;n mining field (Kantor \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e1953\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e1954\u003c/span\u003e; Ilavsk\u0026yacute; \u0026amp; Pol\u0026aacute;k \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e1967\u003c/span\u003e). A slightly extensive work on manganese mineralization at the studied deposit was published by Rojkovič (\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e1999\u003c/span\u003e, \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2000\u003c/span\u003e, \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2001\u003c/span\u003e), who described the basic mineral composition of manganese ores with its probable genetic interpretation.\u003c/p\u003e \u003cp\u003eThis article provides more detailed mineralogical research of the manganese mineralization at the Smoln\u0026iacute;k \u0026ndash; Mal\u0026aacute; Hekerov\u0026aacute; deposit and supplies significant amount of new data focusing on chemical and structural changes in primary phases embedded in manganese ore and associating metacarbonate bodies.\u003c/p\u003e\n\u003ch3\u003eGeological settings and localization\u003c/h3\u003e\n\u003cp\u003eManganese mineralization at the Smoln\u0026iacute;k \u0026ndash; Mal\u0026aacute; Hekerov\u0026aacute; deposit occurs within the Early Palaeozoic, low-grade metamorphic rocks of the Gemeric Unit (Gemericum), situated in the northeastern region of the Spišsko-gemersk\u0026eacute; rudohorie Mountains, eastern Slovakia. The Gemeric Unit comprises several stratigraphic sequences: Lower Palaeozoic basement (Gelnica and Rakovec Groups), Upper Palaeozoic complexes (Ochtin\u0026aacute;, Dobšin\u0026aacute; and Gočaltovo Groups), and a Lower Triassic cover (Kobeliarovo Group) (Bajan\u0026iacute;k et al. \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e1983\u003c/span\u003e). The Lower Paleozoic basement is interpreted to have a riftogenic origin and is associated with the active Gondwana margin (Grecula \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e1982\u003c/span\u003e; Putiš et al. \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e2008\u003c/span\u003e). These sequences were later penetrated by Permian S-type granites (Uher \u0026amp; Broska \u003cspan citationid=\"CR67\" class=\"CitationRef\"\u003e1996\u003c/span\u003e). The Lower Palaeozoic complexes of the Gelnica Group underwent regional metamorphism during the Variscan and Alpine tectonic events, occurring under the greenschist facies conditions (Faryad \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e1991\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e1995\u003c/span\u003e; Voz\u0026aacute;rov\u0026aacute; et al. \u003cspan citationid=\"CR71\" class=\"CitationRef\"\u003e2014\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe Gelnica Group represents low-grade Early Palaeozoic metamorphosed formation with polygenetic and polycyclic development retaining megasequences of flyschoid sedimentation characteristics alongside with syngenetic acid (rhyolite-dacite) and minor basic volcanism. The age of Gelnica Group has been firstly established biostratigraphically indicating the Upper Cambrian to the Lower Devonian (Snopkov\u0026aacute; \u0026amp; Snopko \u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e1979\u003c/span\u003e), later U-Pb SHRIMP dating of zircons extracted from rhyolite metavolcanoclastic rocks defined its age (464\u0026ndash;460 Ma) to the uppermost Middle Ordovician (Voz\u0026aacute;rov\u0026aacute; et al. \u003cspan citationid=\"CR72\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). This Group is divided into three litostratigraphic units, namely Vlachovo, Bystr\u0026yacute; potok and Drnava Formations (Bajan\u0026iacute;k et al. \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e1983\u003c/span\u003e). Lenses with manganese mineralization at the Smoln\u0026iacute;k \u0026ndash; Mal\u0026aacute; Hekerov\u0026aacute; deposit (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) are hosted in the metacarbonate bodies of the Bystr\u0026yacute; potok Formation, surrounded by graphitic and quartz-muscovitic phyllites and metalydites associated with metavolcanoclastic material (tuffs and tuffites) (Bajan\u0026iacute;k et al. \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e1983\u003c/span\u003e; Voz\u0026aacute;rov\u0026aacute; \u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e1993\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe Smoln\u0026iacute;k \u0026ndash; Mal\u0026aacute; Hekerov\u0026aacute; manganese deposit is situated approximately 4 km northwestern of the Smoln\u0026iacute;k town (Gelnica district, Košice region), on the southern slopes of the Bystr\u0026yacute; potok valley, northern to the Mal\u0026aacute; Hekerov\u0026aacute; hill. The manganese locality comprises of multiple surface outcrops mined by small pits and partially or fully collapsed adits with dumps. The manganese mineralization was found in two adits. The northernmost Mang\u0026aacute;nov\u0026aacute; adit with lenticular metacarbonate body with associated manganese mineralization reaching thickness of 2\u0026ndash;3 m, where body was monitored to the surface with thickness up to 4 m, and second adit with small amounts of manganese ore situated further to the west. Southwest at a distance of approximately 200 m, a third adit (referred to as the Magnetitov\u0026aacute; adit) was driven in crystalline limestones, which encountered a position of magnetite 0.2\u0026ndash;0.3 m thick associated with rhodonite and Fe oxides with a high Mn content (up to 27.73 wt.%; Kantor \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e1953\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe main sampling area was localized at the main lower dump with GPS coordinates xx (at altitude x m a. s. l.) and upper dump with GPS coordinates xx (at altitude x m a. s. l.), corresponding to the Manganov\u0026aacute; adit surroundings. Two samples of associating metacarbonate bodies were collected at the nearby outcrop with GPS coordinates 48\u0026deg;44'51.0\"N 20\u0026deg;41'21.8\"E (at the altitude x m a. s. l.). Variable representative samples of manganese ores and associated rocks were collected during the 2019\u0026ndash;2020 period.\u003c/p\u003e \u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eAnalytical methods\u003c/h2\u003e \u003cp\u003eThe representative samples of metamorphosed manganese mineralization were polished to thin sections and mounts, labelled MH-1 to MH-20 from the dumps and nearby metacarbonate outcrop (MH-2 and MH-3). Quantitative chemical (WDS) analyses of studied minerals were obtained using a JEOL-JXA850F field-emission electron microprobe (EMPA) in wavelength-dispersive spectrometry (WDS) mode (Earth Science Institute, Slovak Academy of Sciences, Bansk\u0026aacute; Bystrica, Slovakia). The following conditions were applied: accelerating voltage 15 kV, measuring current 20 nA (silicates, carbonates) and accelerating voltage 20 kV and measuring current 15 nA (sulfides). The beam diameter ranged from 1 to 10 \u0026micro;m, ZAF correction was used. The following standards and X-ray lines were used: albite (Al\u003cem\u003eKα\u003c/em\u003e, Na\u003cem\u003eKα\u003c/em\u003e), Ag (Ag\u003cem\u003eLα\u003c/em\u003e), baryte (S\u003cem\u003eKα\u003c/em\u003e, Ba\u003cem\u003eLα\u003c/em\u003e), Bi\u003csub\u003e2\u003c/sub\u003eSe\u003csub\u003e3\u003c/sub\u003e (Bi\u003cem\u003eMα\u003c/em\u003e) CdTe (Cd\u003cem\u003eLα\u003c/em\u003e), celestine (Sr\u003cem\u003eLα\u003c/em\u003e), CePO\u003csub\u003e4\u003c/sub\u003e (Ce\u003cem\u003eLα\u003c/em\u003e), crocoite (Pb\u003cem\u003eMβ\u003c/em\u003e), Cr\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (Cr\u003cem\u003eKα\u003c/em\u003e), Co (Co\u003cem\u003eKα\u003c/em\u003e), CuFeS\u003csub\u003e2\u003c/sub\u003e (Cu\u003cem\u003eKα\u003c/em\u003e), diopside (Si\u003cem\u003eKα\u003c/em\u003e, Mg\u003cem\u003eKα\u003c/em\u003e, Ca\u003cem\u003eKα\u003c/em\u003e), DyPO\u003csub\u003e4\u003c/sub\u003e (Dy\u003cem\u003eLβ\u003c/em\u003e), fluorapatite (P\u003cem\u003eKα\u003c/em\u003e), fluorite (F\u003cem\u003eKα\u003c/em\u003e), GaAs (As\u003cem\u003eLα\u003c/em\u003e), gahnite (Zn\u003cem\u003eKα\u003c/em\u003e), hematite (Fe\u003cem\u003eKα\u003c/em\u003e), HgTe (Hg\u003cem\u003eLα\u003c/em\u003e), LaPO\u003csub\u003e4\u003c/sub\u003e (La\u003cem\u003eLα\u003c/em\u003e), LiNbO\u003csub\u003e4\u003c/sub\u003e (Nb\u003cem\u003eLα\u003c/em\u003e), LuPO\u003csub\u003e4\u003c/sub\u003e (Lu\u003cem\u003eLα\u003c/em\u003e), Ni\u003csub\u003e2\u003c/sub\u003eSi (Ni\u003cem\u003eKα\u003c/em\u003e), NdPO\u003csub\u003e4\u003c/sub\u003e (Nd\u003cem\u003eLα\u003c/em\u003e), orthoclase (K\u003cem\u003eKα\u003c/em\u003e), PbSe (Se\u003cem\u003eLβ\u003c/em\u003e), PbTe (Te\u003cem\u003eLα\u003c/em\u003e), PrPO\u003csub\u003e4\u003c/sub\u003e (Pr\u003cem\u003eLβ\u003c/em\u003e), rhodonite (Mn\u003cem\u003eKα\u003c/em\u003e), rutile (Ti\u003cem\u003eKα\u003c/em\u003e), Sb\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e3\u003c/sub\u003e (Sb\u003cem\u003eLα\u003c/em\u003e), ScVO\u003csub\u003e4\u003c/sub\u003e (V\u003cem\u003eKα\u003c/em\u003e), SmPO\u003csub\u003e4\u003c/sub\u003e (Sm\u003cem\u003eLβ\u003c/em\u003e), ThO\u003csub\u003e2\u003c/sub\u003e (Th\u003cem\u003eMα\u003c/em\u003e), UO\u003csub\u003e2\u003c/sub\u003e (U\u003cem\u003eMβ\u003c/em\u003e), tugtupite (Cl\u003cem\u003eKα\u003c/em\u003e), YbPO\u003csub\u003e4\u003c/sub\u003e (Yb\u003cem\u003eLα\u003c/em\u003e), and YPO\u003csub\u003e4\u003c/sub\u003e (Y\u003cem\u003eLα\u003c/em\u003e). The detection limit of every element ranged from 0.002\u0026ndash;0.030 wt. %. Elements which were analysed quantitatively and are below the detection limit are not listed in the tables. All chemical analyses are listed in Supplementary Table\u0026nbsp;1. Photographic documentation of relationships between minerals was carried out in the BSE (back scattered electrons) mode. Abbreviations of minerals are defined in Warr (\u003cspan citationid=\"CR74\" class=\"CitationRef\"\u003e2021\u003c/span\u003e).\u003c/p\u003e \u003cp\u003ePowder X-ray diffraction data were collected at room temperature using a Bruker D8 Advance diffractometer equipped with a solid-state LynxEye detector and secondary monochromator producing Cu\u003cem\u003eK\u003c/em\u003eα radiation (Department of Mineralogy and Petrology, National Museum, Prague, Czech Republic). The instrument was operating at 40 kV and 40 mA. In order to minimize the background, the powder samples were placed on the surface of a flat silicon wafer. The powder pattern was collected using a Bragg-Brentano geometry in the range 4\u0026ndash;70\u0026deg; 2θ, step 0.01\u0026deg; and counting time of 8 s per step (total duration of experiment was \u003cem\u003eca\u003c/em\u003e. 12 hours). The positions and intensities of diffraction effects were found and refined using the Pearson VII profile-shape function of the ZDS program package (Ondruš \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e1993\u003c/span\u003e). Unit-cell parameters were refined by the least-squares program of Burnham (\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e1962\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe Raman spectra were obtained using a Thermo Scienctific DXR3xi Raman Imaging microscope at the Natural History Museum (Slovak National Museum) in Bratislava, Slovakia. Two lasers were used during the sample investigation. A 532 nm doubled Nd:YVO\u003csub\u003e4\u003c/sub\u003e DPSS excitation laser, 20 and 50x objective, a 25 \u0026micro;m confocal pinhole, an EMCCD detector with a laser power 10\u0026ndash;20 mW for 0.5 s (2 Hz), 15 scans per cycle. Spectral manipulations were performed using the Thermo Fisher Scientific OMNIC c. 9.11 software package. The Raman spectra were collected in the range 30\u0026ndash;1800 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e \u003c/div\u003e"},{"header":"Results","content":"\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003eTextural characteristics of manganese ore and associated metacarbonate bodies\u003c/h2\u003e \u003cp\u003eThe manganese mineralization at the Smoln\u0026iacute;k \u0026ndash; Mal\u0026aacute; Hekerov\u0026aacute; deposit is hosted within the several meters thick metacarbonate bodies embedded in graphite-muscovitic and quartz-muscovitic phyllites. The metacarbonate is predominantly white to greyish in colour. In areas closely associated with manganese ore, the metacarbonate exhibits a thick black crust along its edges. Internally, it contains stripped zones enriched with light to dark brown spessartine, yellowish titanite and dark greenish stilpnomelane (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea). Close to the contact with manganese ore, the metacarbonate acquires a richer white to slightly pinkish colour, with brown spessartine crystals also visible. The transition from metacarbonate to carbonate-rich manganese mineralization is sharp, marked by a distinct colour change from white to pink (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe silicate-carbonate manganese mineralization appears macroscopically light pink due to fine-grained rhodonite, while coarse-grained rhodochrosite causes its darker pink coloration (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec). Similarly, yellow zones and aggregates result from spessartine accumulations, tephroite tends to cause greyish green massive accumulations, while green hues are caused by chlorites and amphiboles, brownish needle-like zones are formed by caryopilite and greenalite. The manganese ore is rich in polymetallic sulfidic mineralization, characterized by accumulations and aggregates up to several cm in size with a metallic lustre, represented by brass-yellow pyrite, pyrrhotite and chalcopyrite, lead-grey galena and red-brown sphalerite (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed).\u003c/p\u003e \u003cp\u003eThe manganese ore is intersected by an extensive system of veins composed mainly of: (1) rhodonite, carbonate (rhodochrosite, kutnohorite, Mn-rich calcite), quartz and in some area, pyrosmalite-(Mn) and spessartine, (2) rhodochrosite, chlorites, amphiboles, caryopilite and greenalite and (3) polymetallic sulfidic minerals (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec, d). Secondary manganese (hydro)oxides form brown to dark black outer crusts on manganese ore accumulations, they are not part of this study.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eMineral composition of the host metacarbonates\u003c/h3\u003e\n\u003cp\u003eMetacarbonate bodies associating with carbonate-silicate manganese mineralisation are dominantly composed of calcite (up to 80.9 mol.% CaCO\u003csub\u003e3\u003c/sub\u003e molecule) with increased MnCO\u003csub\u003e3\u003c/sub\u003e molecule (up to 18.8 mol.%; 0.17 \u003cem\u003eapfu\u003c/em\u003e Mn) and slightly elevated Fe and Mg (up to 0.01 \u003cem\u003eapfu\u003c/em\u003e) contents (Tab. S1).\u003c/p\u003e \u003cp\u003eThese metacarbonate bodies locally contain significant accumulations of well-developed spessartine crystals up to 5 mm in size, often grouped to the bigger aggregates. Spessartine crystals are light brown to dark orange, with an abundant magnetite and pyrophanite inclusions. In BSE imaging they show no zoning and along the edges they are slightly corroded by partial dissolution (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea). Chemical composition of garnets shows significant presence of spessartine molecule (70.3\u0026ndash;79.9 mol.%) with increased andradite (up to 29.4 mol.%) and minor almandine (up to 4.7 mol.%) molecules (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea). Spessartine contains only elevated amount of Ti (up to 0.04 \u003cem\u003eapfu\u003c/em\u003e) (Tab. S1).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAlongside with spessartine, titanite occurs frequently, with macroscopically light-yellow subhedral crystals up to 0.3 mm in size. Titanite is porous and slightly corroded alongside the edges, it also contains inclusions dominantly composed of calcite and less frequently magnetite (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea). Its chemical composition is close to end-member formula with slightly elevated contents of F (up to 0.13 \u003cem\u003eapfu\u003c/em\u003e), Al (up to 0.10 \u003cem\u003eapfu\u003c/em\u003e), Fe\u003csup\u003e3+\u003c/sup\u003e (up to 0.02 \u003cem\u003eapfu\u003c/em\u003e) and Mn (up to 0.01 \u003cem\u003eapfu\u003c/em\u003e). Content of REE elements investigated in titanite is close to the detection limit (less than 0.01 \u003cem\u003eapfu\u003c/em\u003e) (Tab. S1).\u003c/p\u003e \u003cp\u003eStilpnomelane occurs as acicular elongated crystals, often forming dark brown flakes and aggregates. The crystals reach size up to 3 mm and are closely associated with spessartine. They are sometimes found separately in the calcite masses of metacarbonate body, but most frequently they overgrow spessartine crystals along their edges (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea, b). The chemical composition of stilpnomelane is primarily dominated by Fe (3.92\u0026ndash;4.19 \u003cem\u003eapfu\u003c/em\u003e), partially substituted by Mn (1.90\u0026ndash;2.32 \u003cem\u003eapfu\u003c/em\u003e) and Mg (1.50\u0026ndash;1.68 \u003cem\u003eapfu\u003c/em\u003e). Stilpnomelane is largely depleted in alkali and alkaline earth cations, with only minor amount of Ca\u003csup\u003e2+\u003c/sup\u003e (up to 0.33 \u003cem\u003eapfu\u003c/em\u003e), K\u003csup\u003e+\u003c/sup\u003e (up to 0.15 \u003cem\u003eapfu\u003c/em\u003e), Ba\u003csup\u003e2+\u003c/sup\u003e (up to 0.11 \u003cem\u003eapfu\u003c/em\u003e) and Na\u003csup\u003e+\u003c/sup\u003e (up to 0.02 \u003cem\u003eapfu\u003c/em\u003e), whereas this octahedral position is dominantly vacant (up to 0.68 \u003cem\u003eapfu\u003c/em\u003e) (Tab. S1). Stilpnomelane was identified by X-ray powder diffraction only as a part of mixture with garnet and probably ilmenite. The observed diffraction maxima of stilpnomelane correspond the best with published data for so-called \"\u003cem\u003emanganiferous ferrostilpnomelane\u003c/em\u003e\" (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) from Grythytte, Sweden (Eggleton, Chappell \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e1978\u003c/span\u003e). The observed differences in intensities of individual diffraction maxima are due by the by strong preferred orientation effects.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eX-ray powder diffraction data of stilpnomelane from Smoln\u0026iacute;k \u0026ndash; Mal\u0026aacute; Hekerov\u0026aacute; in comparison with published data for sample from Grythytte, Sweden.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c2\" namest=\"c1\"\u003e \u003cp\u003ethis paper\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003eEggleton, Chappell (\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e1978\u003c/span\u003e)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003ed\u003c/em\u003e\u003csub\u003e\u003cem\u003eobs\u003c/em\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eI\u003c/em\u003e\u003csub\u003e\u003cem\u003eobs\u003c/em\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u003cem\u003ed\u003c/em\u003e\u003csub\u003e\u003cem\u003eobs\u003c/em\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u003cem\u003eI\u003c/em\u003e\u003csub\u003e\u003cem\u003eobs\u003c/em\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e12.216\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e100.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e12.15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e7.123\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e7.21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e6.088\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e6.07\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e5.525\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5.51\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e4.781\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e4.77\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e4.382\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e4.38\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e4.054\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e14.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e4.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e70\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3.82\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3.60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e3.038\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e9.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3.035\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2.729\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.735\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2.646\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.646\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2.580\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.583\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2.4347\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.442\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2.3597\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.362\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2.1987\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.202\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2.1204\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.121\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.968\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1.8964\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.894\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1.6921\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.693\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1.5913\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.596\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eFluorapatite occurs rarely as euhedral crystals and grains up to 8 \u0026micro;m in size. Content of the majority elements is close to ideal end-member formula, fluorapatite only shows slightly elevated content of Mn (up to 0.06 apfu), content of ΣREE (Ce\u003csup\u003e3+\u003c/sup\u003e+La\u003csup\u003e3+\u003c/sup\u003e+Nd\u003csup\u003e3+\u003c/sup\u003e+Pr\u003csup\u003e3+\u003c/sup\u003e) does not exceed 0.01 \u003cem\u003eapfu\u003c/em\u003e (Tab. S1). From the polymetallic sulfidic mineralization, only pyrite was identified in metacarbonates associating with all minerals forming euhedral to anhedral crystals and aggregates.\u003c/p\u003e\n\u003ch3\u003eMineral composition of manganese ore\u003c/h3\u003e\n\u003cp\u003eCarbonates represent the most common mineral group, which mostly forms carbonate-silicate mineralisation at the studied locality. They predominantly occur as massive fine-grained aggregates, which form matrix, veins and rarely inclusions (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea, b, f, g).\u003c/p\u003e \u003cp\u003eCarbonates in the matrix consist of Ca-rich rhodochrosite and kutnohorite. The chemical composition of rhodochrosite shows up to 84.8 mol.% MnCO\u003csub\u003e3\u003c/sub\u003e molecule, with relatively high content of CaCO\u003csub\u003e3\u003c/sub\u003e (up to 28.3 mol.%) and FeCO\u003csub\u003e3\u003c/sub\u003e (5.3 mol.%) molecules. Similarly, in kutnohorite enrichment in Ca leads to an increase in CaCO\u003csub\u003e3\u003c/sub\u003e (up to 68.1 mol.%) and a decrease in MnCO\u003csub\u003e3\u003c/sub\u003e (up to 33.8 mol.%) molecules, along with slightly elevated contents of FeCO\u003csub\u003e3\u003c/sub\u003e (up to 3.3 mol.%) and MgCO\u003csub\u003e3\u003c/sub\u003e (up to 1.8 mol.) molecules (Tab. S1).\u003c/p\u003e \u003cp\u003eVein-type carbonates are the dominant constituent of carbonate-quartz-rhodonite veins, where they mostly occur as rhodochrosite, to a lesser extent as kutnohorite. Rhodochrosite forms up to 0.5 mm thin needle-like crystals grouped to the bigger aggregates. It locally shows elevated content of CaCO\u003csub\u003e3\u003c/sub\u003e molecule (up to 21.9 mol.%), but typically it has the highest content of MnCO\u003csub\u003e3\u003c/sub\u003e molecule observed in this study (up to 94.7 mol. %). It also shows a slightly increased FeCO\u003csub\u003e3\u003c/sub\u003e content (up to 7.24 mol. %) (Tab. S1).\u003c/p\u003e \u003cp\u003eThe third type of carbonate occurs within the polycrystalline spessartine crystals, separating their inner and other zones (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec-f). This carbonate is classified as Mn-rich calcite, containing up to 78.4 mol.% of CaCO\u003csub\u003e3\u003c/sub\u003e molecule and increased content of MnCO\u003csub\u003e3\u003c/sub\u003e (up to 22.0 mol.%) molecule (Tab. S1).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe most common primary silicate minerals identified in the manganese mineralization belong to the rhodonite group, characterized by the general structural formula \u003csup\u003eVII\u003c/sup\u003e\u003cem\u003eM\u003c/em\u003e(5)\u003csup\u003eVI\u003c/sup\u003e\u003cem\u003eM\u003c/em\u003e(1)\u003csup\u003eVI\u003c/sup\u003e\u003cem\u003eM\u003c/em\u003e(2)\u003csup\u003eVI\u003c/sup\u003e\u003cem\u003eM\u003c/em\u003e(3)\u003csup\u003eVI\u003c/sup\u003e\u003cem\u003eM\u003c/em\u003e4)[Si\u003csub\u003e5\u003c/sub\u003eO\u003csub\u003e15\u003c/sub\u003e] (Shchipalkina et al. \u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). These minerals were identified as rhodonite (\u003csup\u003e\u003cem\u003eM4\u003c/em\u003e\u003c/sup\u003eMn\u003csup\u003e2+\u003c/sup\u003e\u0026gt;0.5) and Fe-rich rhodonite, seamlessly transitioning into ferrorhodonite (\u003csup\u003e\u003cem\u003eM\u003c/em\u003e4\u003c/sup\u003eFe\u003csup\u003e2+\u003c/sup\u003e\u0026gt;0.5). Rhodonite group minerals form alongside with rhodochrosite main silicate-carbonate mineralization in matrix, where rhodonites occurs as anhedral to subhedral crystals up to 3 mm in size, often grouped to the massive aggregates (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea). Rhodonite was less often identified in the veins overgrowing with rhodochrosite and quartz. In BSE images, no visible zoning within the rhodonite-ferrorhodonite fine-grained masses was observed. The peak positions in both experimental X-ray powder patterns (Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e) agree with data published for ferrorhodonite from type locality (Shchipalkina et al. \u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e2017\u003c/span\u003e) as well as with those calculated based on Lazy Pulverix program (Yvon et al. \u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e1977\u003c/span\u003e) from the crystal structure of this mineral (Shchipalkina et al. \u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). Differences between observed and calculated diffraction intensity are caused by preferred orientation and other textural effects. The refined unit-cell parameters, compared with published data for members of rhodonite group are given in the Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eX-ray powder diffraction data of rhodonite group minerals from Smoln\u0026iacute;k \u0026ndash; Mal\u0026aacute; Hekerov\u0026aacute;\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"10\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eFe-rich rhodonite\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colspan=\"3\" nameend=\"c7\" namest=\"c5\"\u003e \u003cp\u003eferrorhodonite\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eI\u003c/em\u003e\u003csub\u003e\u003cem\u003eobs\u003c/em\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003ed\u003c/em\u003e\u003csub\u003e\u003cem\u003eobs\u003c/em\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u003cem\u003ed\u003c/em\u003e\u003csub\u003e\u003cem\u003ecalc\u003c/em\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u003cem\u003eI\u003c/em\u003e\u003csub\u003e\u003cem\u003eobs\u003c/em\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u003cem\u003ed\u003c/em\u003e\u003csub\u003e\u003cem\u003eobs\u003c/em\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003cem\u003ed\u003c/em\u003e\u003csub\u003e\u003cem\u003ecalc\u003c/em\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e\u003cem\u003eh\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e\u003cem\u003ek\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e\u003cem\u003el\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e18\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e7.153\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e7.134\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e7.155\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e7.141\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e6.686\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e6.672\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e34\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e6.693\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e6.679\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e33\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e4.774\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e4.773\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e24\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e4.783\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e4.778\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e4.129\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e4.129\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e4.138\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e4.133\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3.685\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3.684\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3.691\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e3.687\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e33\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3.569\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3.567\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e38\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3.572\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e3.570\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3.415\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3.417\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e 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align=\"left\" colname=\"c7\"\u003e \u003cp\u003e3.349\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e31\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3.337\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3.336\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e42\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3.341\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e3.340\u003c/p\u003e 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align=\"left\" colname=\"c9\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e17\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3.098\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3.097\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3.101\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e3.100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-2\u003c/p\u003e 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align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.812\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.811\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.815\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.814\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.788\u003c/p\u003e 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align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e16\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.658\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.658\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e32\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.601\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.601\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e 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align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.4610\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.4598\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.4303\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.4306\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e 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align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.3889\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.3788\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.3781\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.3807\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e 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align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.2251\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.2246\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e24\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.2266\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.2263\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0\u003c/p\u003e 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align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e12\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.1574\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.1579\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.1597\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.1600\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1\u003c/p\u003e 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align=\"left\" colname=\"c1\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.0962\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.0971\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.0986\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.0988\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e11\u003c/p\u003e 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colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e14\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.8708\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.8709\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.8687\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.8692\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.8436\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.8451\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e 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colname=\"c7\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.7753\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.7749\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.7766\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.7765\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.7481\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.7482\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.7491\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.7496\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0\u003c/p\u003e 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align=\"left\" colname=\"c10\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.6653\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.6652\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e45\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.6665\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.6668\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e 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\u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.6398\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.6399\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.6410\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.6409\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.6057\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.6057\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.6062\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.6069\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.5910\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.5910\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.5921\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.5926\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.5863\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.5860\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.5871\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.5871\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.5152\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.5151\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.5160\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.5165\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.4783\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.4786\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.4794\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.4800\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e22\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.4321\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.4321\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e16\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.4332\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.4335\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.3871\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.3869\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.3878\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.3880\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eUnit-cell parameters for members of rhodonite group (for triclinic space group \u003cem\u003eP\u003c/em\u003e-1).\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eferrorhodonite\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eFe-rich rhodonite\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eferrorhodonite\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003erhodonite\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003evittinkiite\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003ethis paper\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003ethis paper\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eShchipalkina et al. (\u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e2017\u003c/span\u003e)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eShchipalkina et al. (\u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e2019\u003c/span\u003e)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eShchipalkina et al. (\u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e2019\u003c/span\u003e)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003ea\u003c/em\u003e [\u0026Aring;]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e6.7079(8)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e6.7015(6)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e6.6766(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e6.67\u0026ndash;6.70\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e6.70\u0026ndash;6.71\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eb\u003c/em\u003e [\u0026Aring;]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e7.6840(14)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e7.6771(11)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e7.6754(6)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e7.62\u0026ndash;7.68\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e7.62\u0026ndash;7.64\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003ec\u003c/em\u003e [\u0026Aring;]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e11.830(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e11.8227(18)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e11.803(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e11.78\u0026ndash;11.84\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e11.84\u0026ndash;11.86\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eα [\u003csup\u003eo\u003c/sup\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e105.629(11)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e105.612(9)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e105.501(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e105.4-105.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e105.6-105.7\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eβ [\u003csup\u003eo\u003c/sup\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e92.302(12)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e92.314(9)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e92.275(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e92.4\u0026ndash;92.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e92.4\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eγ [\u003csup\u003eo\u003c/sup\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e93.995(11)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e94.001(8)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e93.919(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e93.9\u0026ndash;94.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e94.2\u0026ndash;94.3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eV\u003c/em\u003e [\u0026Aring;\u003csup\u003e3\u003c/sup\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e584.7(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e583.28(16)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e580.44(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e577\u0026ndash;580\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e579\u0026ndash;580\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eChemical composition of rhodonite group minerals show \u003csup\u003e\u003cem\u003eM\u003c/em\u003e5\u003c/sup\u003eCa/(Ca\u0026thinsp;+\u0026thinsp;Mn) ratio in the range 0.52\u0026ndash;0.95, while positions \u003cem\u003eM\u003c/em\u003e1, \u003cem\u003eM\u003c/em\u003e2 and \u003cem\u003eM\u003c/em\u003e3 are fully occupied by Mn\u003csup\u003e2+\u003c/sup\u003e. Rhodonite from matrix generally tends to be at the position \u003cem\u003eM\u003c/em\u003e4 enriched in Fe\u003csup\u003e2+\u003c/sup\u003e (up to 0.95 \u003cem\u003eapfu\u003c/em\u003e) within the \u003csup\u003e\u003cem\u003eM\u003c/em\u003e4\u003c/sup\u003eMn/(Mn\u0026thinsp;+\u0026thinsp;Fe) ratio in the range 0.03\u0026ndash;0.49. On the other side, rhodonite from veins shows enrichment in Mn\u003csup\u003e2+\u003c/sup\u003e (up to 0.88 \u003cem\u003eapfu\u003c/em\u003e) with \u003csup\u003e\u003cem\u003eM\u003c/em\u003e4\u003c/sup\u003eMn/(Mn\u0026thinsp;+\u0026thinsp;Fe) ratio in 0.51\u0026ndash;0.78 interval. Rhodonite group minerals from matrix tend to have slightly elevated content of Mg (up to 0.35 \u003cem\u003eapfu\u003c/em\u003e) compared to those from veins (up to 0.01 \u003cem\u003eapfu\u003c/em\u003e) (Tab. S1).\u003c/p\u003e \u003cp\u003eSpessartine is another frequent component in manganese carbonate-silicate ore, forming euhedral to anhedral crystals up to 5 mm in size, often grouped to the bigger aggregates. Spessartine aggregates macroscopically appears as light pink to light orange masses, occurring both in the matrix and veins. Garnets identified in the manganese ore can be categorised into three types based on their appearance, chemical composition and location in ore (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea).\u003c/p\u003e \u003cp\u003eThe first type of spessartine occurs is dominant component of manganese ore identified in matrix. It forms anhedral to subhedral crystals grouped into aggregates (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec, e, g, h). This type contains numerous inclusions, including quartz, magnetite, pyrophanite, pyrosmalite-(Mn), tephroite and rhodochrosite (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed). Its chemical composition is relatively stable, with spessartine molecule ranging from 82.6 to 93.8 mol.%, slightly elevated andradite molecule (up to 17.2 mol. %) and almandine (up to 0.5 mol. %) molecules are also present (Tab. S1).\u003c/p\u003e \u003cp\u003eThe second type of spessartine occurs in veins, often associated with rhodochrosite and locally with rhodonite. Veins dominated by spessartine aggregates are macroscopically light orange and can reach up to 1.3 cm in thickness. This type has fewer inclusions, mostly formed by rhodochrosite. Its chemical composition significantly differs by reduced, but still dominant, spessartine molecule (64.2\u0026ndash;77.9 mol.%) and increased andradite (up to 35.7 mol.%) and almandine (up to 2.1 mol.%) molecules.\u003c/p\u003e \u003cp\u003eThe third type of spessartine is represented by polycrystalline aggregates composed of central parts zoned along the edges and newly formed rims separated by thin calcite zone (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec-f). In some cases, the central parts or zones are completely absent, leaving only the newly formed rim identifiable (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec). The central parts (Sps1) has the biggest content of spessartine molecule (up to 89.4 mol.%) with slightly elevated andradite (up to 15.8 mol.%) and almandine (up to 0.3 mol.%) molecules. Surrounding the central sps1 zone, the outer Sps2 zone has lowered content of spessartine (up to 73.3 mol.%) and increased andradite (up to 37.2 mol.%) and almandine (up to 0.3 mol.%) molecules. This zone is porous and in BSE imaging can be differentiated by change in colour. The third garnet outer rim zone (Sps3) is separated from the inner two zones by in average 80 \u0026micro;m thick zone of Mn-rich calcite. The Sps3 zone retains the typical garnet growth shape and consists mainly of spessartine (up to 78.1 mol.%) with elevated andradite (up to 32.9 mol.%) and almandine (up to 9.5 mol.%) molecules (Tab. S1).\u003c/p\u003e \u003cp\u003eTephroite is another abundant mineral in the manganese ore, where it occurs in two forms. The first most common type creates elongated, macroscopically reddish-brow crystals up to 2 mm long and 50 \u0026micro;m thick, closely associated with rhodonite and pyrosmalite-(Mn) embedded in rhodochrosite (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb), rhodonite locally overgrows tephroite. This type of tephroite is formed by up to 90.7 mol.% of tephroite molecule (representing up to 1.83 \u003cem\u003eapfu\u003c/em\u003e Mn\u003csup\u003e2+\u003c/sup\u003e), with minor fayalite (up to 8.7 mol.%; 0.18 \u003cem\u003eapfu\u003c/em\u003e Fe\u003csup\u003e2+\u003c/sup\u003e) and forsterite (up to 2.0 mol.%; 0.04 \u003cem\u003eapfu\u003c/em\u003e Mg\u003csup\u003e2+\u003c/sup\u003e) molecules. The second type of tephroite forms up to 15 \u0026micro;m anhedral inclusions in spessartine, associated with pyrosmalite-(Mn), magnetite and pyrophanite (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed). Chemical composition differs by significant increase in fayalite molecule (up to 31 mol.%; 0.75 \u003cem\u003eapfu\u003c/em\u003e Fe\u003csup\u003e2+\u003c/sup\u003e) and decrease in tephroite molecule (up to 79.1 mol.%; 1.58 \u003cem\u003eapfu\u003c/em\u003e Mn\u003csup\u003e2+\u003c/sup\u003e), while forsterite molecule remains similar to the first type of tephroite (up to 2.5 mol.%; up to 0.05 \u003cem\u003eapfu\u003c/em\u003e Mg\u003csup\u003e2+\u003c/sup\u003e) (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb, Tab. S1).\u003c/p\u003e \u003cp\u003ePyrosmalite-(Mn) occurs commonly in three forms. Firstly, it creates accumulations of weakly zoned crystals up to 10 mm in size, macroscopically forming light yellow aggregates in pinkish manganese ore associated mostly with rhodonite, rhodochrosite, tephroite and spessartine (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec). Crystals show weak zoning caused by content changes of Fe and Mn. Chemical composition of this type of pyrosmalite-(Mn) shows the highest amount of Mn (up to 7.50 \u003cem\u003eapfu\u003c/em\u003e) and the lowest content of Fe (1.74 \u003cem\u003eapfu\u003c/em\u003e). The second type is represented by subhedral grains of pyrosmalite-(Mn) forming inclusions in spessartine associated with tephroite, magnetite and pyrophanite (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed). Chemical composition of these inclusions differs by lowered content of Mn (up to 5.76 \u003cem\u003eapfu\u003c/em\u003e) and increased content of Fe (up to 2.39 \u003cem\u003eapfu\u003c/em\u003e). The third type of pyrosmalite-(Mn) occurs in veins and local accumulations with relatively low Mn (up to 4.82\u0026ndash;5.81 \u003cem\u003eapfu\u003c/em\u003e) and elevated Fe (up to 2.97 \u003cem\u003eapfu\u003c/em\u003e) contents (Tab. S1). Substitution of Fe vs Mn shows a linear trend with increasing Fe in vein-type pyrosmalite compared to those pyrosmalite-(Mn) from matrix (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec).\u003c/p\u003e \u003cp\u003eAmphibole supergroup minerals, with general formula AB\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e5\u003c/sub\u003eT\u003csub\u003e8\u003c/sub\u003eO\u003csub\u003e22\u003c/sub\u003eW\u003csub\u003e2\u003c/sub\u003e (Hawthorne et al. \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2012\u003c/span\u003e), are at the studied locality represented by clino-suenoite (☐Mn\u003csup\u003e2\u0026thinsp;+\u003c/sup\u003e\u0026thinsp;\u003csub\u003e2\u003c/sub\u003eMg\u003csub\u003e5\u003c/sub\u003eSi\u003csub\u003e8\u003c/sub\u003eO\u003csub\u003e22\u003c/sub\u003e(OH)\u003csub\u003e2\u003c/sub\u003e) (Oberti et al. \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2018\u003c/span\u003e), clino-ferro-suenoite (☐Mn\u003csup\u003e2\u0026thinsp;+\u003c/sup\u003e\u0026thinsp;\u003csub\u003e2\u003c/sub\u003eFe\u003csup\u003e2\u0026thinsp;+\u003c/sup\u003e\u0026thinsp;\u003csub\u003e5\u003c/sub\u003eSi\u003csub\u003e8\u003c/sub\u003eO\u003csub\u003e22\u003c/sub\u003e(OH)\u003csub\u003e2\u003c/sub\u003e) (Holtstam et al. \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2024\u003c/span\u003e) as well as actinolite (☐Ca\u003csub\u003e2\u003c/sub\u003eMg\u003csub\u003e4.5\u0026minus;2.5\u003c/sub\u003eFe\u003csub\u003e0.5\u0026minus;2.5\u003c/sub\u003e)Si\u003csub\u003e8\u003c/sub\u003eO\u003csub\u003e22\u003c/sub\u003e(OH)\u003csub\u003e2\u003c/sub\u003e). Amphiboles in the manganese ore occur as greenish to dark brown acicular prismatic crystals with a rhombic cross-section, grouped into larger aggregates. These amphiboles can be found in both the matrix and veins, typically measuring approximately 50 \u0026micro;m to 0.5 mm in size, though locally some crystals can reach up to 3 mm in size. BSE imaging reveals significant zoning, where the mostly outer lightest parts are composed of clino-ferro-suenoite and the mostly inner darker zones are formed by clino-suenoite (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ee). Actinolite, on the other hand, mostly occurs in the form of well-developed crystals grouped into the aggregates within the veins or local massive accumulation. Actinolite shows only weak zoning and it consistently overgrows with other amphiboles and vein-type rhodochrosite along the crystal edges (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec-f).\u003c/p\u003e \u003cp\u003eThe chemical composition of clino-suenoite at the crystallochemical position \u003cem\u003eB\u003c/em\u003e shows dominant content of Mn\u003csup\u003e2+\u003c/sup\u003e (up to 1.90 \u003cem\u003eapfu\u003c/em\u003e), while position \u003cem\u003eC\u003c/em\u003e dominantly occupied by Mg (up to 3.55 \u003cem\u003eapfu\u003c/em\u003e). Similarly, in clino-ferro-suenoite position \u003cem\u003eB\u003c/em\u003e is predominantly occupied by Mn (up to 1.96 \u003cem\u003eapfu\u003c/em\u003e) and the position \u003cem\u003eC\u003c/em\u003e is dominantly composed of Fe\u003csup\u003e2+\u003c/sup\u003e (up to 3.54 \u003cem\u003eapfu\u003c/em\u003e). In both amphiboles, the \u003csup\u003e\u003cem\u003eB\u003c/em\u003e\u003c/sup\u003eCa content does not exceed 0.47 \u003cem\u003eapfu\u003c/em\u003e. Additionally, a locally increased content of F\u003csup\u003e\u0026minus;\u003c/sup\u003e (up to 0.38 \u003cem\u003eapfu\u003c/em\u003e) was observed at the position \u003cem\u003eW\u003c/em\u003e (Tab. S1).\u003c/p\u003e \u003cp\u003eOn the other hand, the chemical composition of actinolite is characterized by dominant Mg (up to 4.02 \u003cem\u003eapfu\u003c/em\u003e) at the position \u003cem\u003eB\u003c/em\u003e, compared to lower Fe\u003csup\u003e2+\u003c/sup\u003e (up to 1.22 \u003cem\u003eapfu\u003c/em\u003e) and Mn (up to 0.54 \u003cem\u003eapfu\u003c/em\u003e) contents. The position \u003cem\u003eC\u003c/em\u003e is primarily composed of Ca (up to 1.88 \u003cem\u003eapfu\u003c/em\u003e) over Mn (up to 0.75 \u003cem\u003eapfu\u003c/em\u003e). Similarly, an increased F\u003csup\u003e\u0026minus;\u003c/sup\u003e content (up to 0.41 \u003cem\u003eapfu\u003c/em\u003e) was also observed (Tab. S1).\u003c/p\u003e \u003cp\u003eMinerals of the kaolinite-serpentine group were identified as caryopilite (Mn\u003csup\u003e2\u0026thinsp;+\u003c/sup\u003e\u0026thinsp;\u003csub\u003e3\u003c/sub\u003eSi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e(OH)\u003csub\u003e4\u003c/sub\u003e) and greenalite (Fe\u003csup\u003e2+\u003c/sup\u003e,Fe\u003csup\u003e3+\u003c/sup\u003e)\u003csub\u003e2\u0026minus;3\u003c/sub\u003eSi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e(OH)\u003csub\u003e4\u003c/sub\u003e). Both minerals were mostly observed as phases crystallized along the edges of predominantly rhodonite crystals (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ef), to a lesser content on the other silicates, or as fine needle-like felt aggregates forming up to 0.1 mm thick dark brown veins. Caryopilite exhibits an Fe/(Fe\u0026thinsp;+\u0026thinsp;Mn) ratio in the range of 0.24 to 0.29, while greenalite is in the range 0.50 to 0.55 (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed). Both minerals show elevated content of Mg with up to 0.29 \u003cem\u003eapfu\u003c/em\u003e in caryopilite and up to 0.52 \u003cem\u003eapfu\u003c/em\u003e in greenalite. Caryopilite has a R/Si ratio (R\u0026thinsp;=\u0026thinsp;Mn\u0026thinsp;+\u0026thinsp;Fe\u0026thinsp;+\u0026thinsp;Mg\u0026thinsp;+\u0026thinsp;Al) in the range of 1.23\u0026ndash;1.30, whereas greenalite shows a slightly higher range of 1.29\u0026ndash;1.42. Furthermore, caryopilite has slightly elevated content of Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e (up to 0.08 \u003cem\u003eapfu\u003c/em\u003e) (Tab. S1). Greenalite and caryopilite Raman spectra are given in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e. The main bands observed (in wavenumbers) for greenalite are 185, 318, 400, 490, 633, 1028 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and caryopilite are 190, 399, 487, 641 and 1027 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eMinerals of chlorite group occur frequently, they form fibrous crystals up to 30 \u0026micro;m in size grouped to macroscopically bigger dark green acicular aggregates in narrow veins associated with Mn-rich carbonates and quartz. They were also observed associated with rhodochrosite replacing spessartine (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eg). In BSE imaging they are slightly zoned. Chemical composition reflects their variability in content of Fe, Mg and Mn. Clinochlore has Mg/(Mg\u0026thinsp;+\u0026thinsp;Fe) ratio in the range 0.51\u0026ndash;0.59 with slightly elevated content of Mn (up to 0.30 \u003cem\u003eapfu\u003c/em\u003e), chamosite with Mg/(Mg\u0026thinsp;+\u0026thinsp;Fe) ratio in the range 0.17\u0026ndash;0.20 shows significantly increased content of Mn (up to 0.76 \u003cem\u003eapfu\u003c/em\u003e), due to which, in some analyses, pennantite substitution (up to 0.76 \u003cem\u003eapfu\u003c/em\u003e Mn) is present more than clinochlore substitution (up to 0.73 \u003cem\u003eapfu\u003c/em\u003e Mg) (Tab. S1).\u003c/p\u003e \u003cp\u003eMagnetite is the most common accessory mineral in manganese ore. It forms anhedral to subhedral crystals in rhodonite-rhodochrosite matrix, locally magnetite is present in the form of inclusions in spessartine (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed). It was also identified in the nearby Magnetitov\u0026aacute; adit forming magnetite bodies. Chemical composition is close to the ideal end-member formula with slightly elevated content of Mn (up to 0.05 \u003cem\u003eapfu\u003c/em\u003e) (Tab. S1).\u003c/p\u003e \u003cp\u003ePyrophanite belongs to accessory minerals in manganese ores, where it occurs in the form of inclusions in other minerals, mostly in spessartine or rhodonite. It forms elongated subhedral crystals up to 30 \u0026micro;m in size. Pyrophanite was rarely found in one sample in the form of well-developed and strongly zoned crystals up to 0.2 mm in size associated with spessartine, rhodonite, rhodochrosite and pyrosmalite-(Mn) (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eh). Zonality is caused by relatively strong substitution of Mn and Fe, where pyrophanite molecule occurs within the range 67.45\u0026ndash;93.82 mol.% (0.65\u0026ndash;0.93 \u003cem\u003eapfu\u003c/em\u003e Mn) compensated with ilmenite molecule in the range 6.78\u0026ndash;32.55 mol.% (0.06\u0026ndash;0.32 \u003cem\u003eapfu\u003c/em\u003e Fe) (Tab. S1).\u003c/p\u003e \u003cp\u003eAlabandite is rare mineral identified in rhodochrosite assemblages in carbonate-silicate matrix, where it forms anhedral aggregates up to 0.5 mm in size. Macroscopically alabandite is black colour with metallic lustre. It contains a large amount of pyrrhotite inclusions up to 10 \u0026micro;m in size (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea). Chemical composition is characteristic with composition close to the ideal end-member formula with Mn (0.99\u0026ndash;1.02 \u003cem\u003eapfu\u003c/em\u003e) and S (0.99\u0026ndash;1.01 \u003cem\u003eapfu\u003c/em\u003e). Alabandite contains up to 5.9 wt.% of FeO (up to 0.09 \u003cem\u003eapfu\u003c/em\u003e Fe, respectively).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003ePolymetallic sulfidic mineralisation in carbonate-silicate manganese ore is relatively common and is represented by pyrite, pyrrhotite, chalcopyrite, galena and sphalerite (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb). Minerals occur in the form of isolated crystals and polyphase aggregates embedded in the ore matrix and veins. Single and well-terminated crystals reach size up to 1 cm, with even bigger aggregates. No significant zoning in BSE was observed, also reflecting its homogenous chemical composition (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ec, d). Chemical composition of all sulfides is close to the end-member formula with Ni, Co, Bi, Hg or Sb components reaching less than 0.01 \u003cem\u003eapfu\u003c/em\u003e. Only in sphalerite elevated content of Mn (up to 0.02 \u003cem\u003eapfu\u003c/em\u003e) was observed (Tab. S1).\u003c/p\u003e"},{"header":"Discussion","content":"\u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003eOrigin of metacarbonate bodies and manganese mineralization\u003c/h2\u003e \u003cp\u003eMetacarbonates originally formed as organodetritic allodapic limestones, that were part of hemipellagic sediments (Bajan\u0026iacute;k et al. \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e1983\u003c/span\u003e; Kov\u0026aacute;čik \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2004\u003c/span\u003e) and were later metamorphosed and deformed during the Variscan and Alpine development of the Spišsko-gemersk\u0026eacute; rudohorie Mts. (Grecula et al. \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e1995\u003c/span\u003e; Voz\u0026aacute;rov\u0026aacute; et al. \u003cspan citationid=\"CR71\" class=\"CitationRef\"\u003e2014\u003c/span\u003e, \u003cspan citationid=\"CR72\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). Their lamination results from differences in composition, structure, and mineral grain size, as well as metamorphic deformation (Kobulsk\u0026yacute; et al. \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2006\u003c/span\u003e; Grecula et al. \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2011\u003c/span\u003e), similar to the features observed in the studied metacarbonates associating with manganese ore (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea). The mineral composition of metacarbonates reflects their original pre-metamorphic composition, which includes significant content of pelitic and volcanoclastic material. This composition was subsequently modified by metamorphic and, in some cases, metasomatic processes (Grecula et al. \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2011\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eMetacarbonates from Gelnica Group often contain manganese ore lenses, locally associated with magnetite bodies. Rojkovič (\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e1999\u003c/span\u003e, \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2000\u003c/span\u003e, \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2001\u003c/span\u003e) proposed that manganese migrated from the deep, oxygen-poor regions of the ocean to shallower, oxygen-rich waters, where it formed basic manganese oxides and hydroxides, serving as a primary precursor to more complex carbonates and silicates. Kantor (\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e1954\u003c/span\u003e) and Grecula et al. (\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e1995\u003c/span\u003e) suggested that mineralization resulted from volcano-sedimentary processes linked to basaltic volcanic activity. These processes, accompanied by hydrothermal vent exhalations produced Fe, Mn, SiO₂, and H₂S, indicating a significant influence of submarine volcanic and hydrothermal fluids (Ilavsk\u0026yacute; \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e1957\u003c/span\u003e; Grecula et al. \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e1995\u003c/span\u003e) or a volcanogenic-exhalative origin (M\u0026uuml;cke et al. \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e2001\u003c/span\u003e; M\u0026uuml;cke \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e2005\u003c/span\u003e). Additionally, diagenetic processes involving organic material (metamorphosed equivalents identified in associating lydites and graphite-muscovitic phyllites) contributed to manganese precipitation (Rojkovič \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e1999\u003c/span\u003e, \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2000\u003c/span\u003e, \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2001\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe average calculated temperature of clinochlore crystallization in association with muscovite in metacarbonates acquired by two chlorite geothormometers reaches the interval 357\u0026ndash;362\u0026thinsp;\u0026plusmn;\u0026thinsp;6\u0026deg;C (Myšľan \u0026amp; Ružička, \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Sassi \u0026amp; Voz\u0026aacute;rov\u0026aacute; (\u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e1987\u003c/span\u003e) and Mazzoli \u0026amp; Voz\u0026aacute;rov\u0026aacute; (\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e1989\u003c/span\u003e) estimated greenschist facies conditions in the range of 300\u0026ndash;440\u0026deg;C at the 3\u0026ndash;5 kbar. Associated metacarbonates and manganese mineralization underwent metamorphism at 375\u0026ndash;420\u0026deg;C under 3.5 kbar (Faryad \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e1991\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e1994\u003c/span\u003e; Rojkovič \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e1999\u003c/span\u003e), as calculated for the Čučma-Čierna baňa manganese deposit, suggesting similar conditions at the studied locality.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eMineral composition of metacarbonate bodies\u003c/h3\u003e\n\u003cp\u003eIn the metacarbonates of the Gelnica Group, except of calcite, mostly chlorite group minerals (chamosite and clinochlore), muscovite, feldspars, quartz and accessory fluorapatite and rutile were identified (Myšľan \u0026amp; Ružička, \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Only metacarbonates closely associated with manganese ores at the Čučma deposit contain diopside and grossular (Ružička et al. \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). The elevated manganese content in these metacarbonates suggests deeper-water sedimentation conditions with subsequent manganese incorporation, genetically linked to the oceanic environment (Voz\u0026aacute;rov\u0026aacute; \u0026amp; Ivanička \u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e1993\u003c/span\u003e). At the studied locality, content of MnCO\u003csub\u003e3\u003c/sub\u003e molecule in metacarbonate bodies is elevated (up to 29.7 mol.%), suggesting close relation of manganese and carbonate production.\u003c/p\u003e \u003cp\u003eMetacarbonates at the studied deposit contain an accumulations of spessartine, titanite, stilpnomelane and locally hydrothermal pyrite. In titanite, the Ti content is slightly decreased (0.89\u0026ndash;0.96 \u003cem\u003eapfu\u003c/em\u003e) due to the substitution (Al,Fe\u003csup\u003e3+\u003c/sup\u003e) + (OH,F)\u003csup\u003e\u0026minus;\u003c/sup\u003e \u0026harr; Ti\u003csup\u003e4+\u003c/sup\u003e + O\u003csup\u003e2\u0026minus;\u003c/sup\u003e, as evidenced by the small increase in F content (up to 1.3 wt.%; 0.13 \u003cem\u003eapfu\u003c/em\u003e). Low compositional range of Al\u0026thinsp;+\u0026thinsp;Fe\u003csup\u003e3+\u003c/sup\u003e (0.05\u0026ndash;0.12 \u003cem\u003eapfu\u003c/em\u003e) and F (0.05\u0026ndash;0.13 \u003cem\u003eapfu\u003c/em\u003e) (Tab. S1) is typical for low-pT titanites rather than those high-pT (F\u0026thinsp;\u0026gt;\u0026thinsp;0.50 \u003cem\u003eapfu\u003c/em\u003e) (Enami et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e1993\u003c/span\u003e). Spessartine in metacarbonate closely associated with manganese ore was probably formed through decarbonation and dehydration reactions based on reactions with minerals embedded in precursor Mn-rich carbonates, quartz and clay minerals. Pure spessartine formation begins during the low-pressure and temperature prograde metamorphism at the as low as ~\u0026thinsp;300\u0026ordm;C (Theye et al. \u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e1996\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eStilpnomelane is restricted mineral of the mostly low grade metamorphic conditions (Miyano \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e1982\u003c/span\u003e; Feininger \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e1984\u003c/span\u003e; Wang et al. \u003cspan citationid=\"CR73\" class=\"CitationRef\"\u003e2023\u003c/span\u003e, etc.) in various types of rocks forming during both prograde and retrograde metamorphism, only rarely it occurs in blueschist facies (Potel et al. \u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e2006\u003c/span\u003e). Li et al. (\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2000\u003c/span\u003e) suggested, that stilpnomelane formed via replacing chlorite and preserving the primary grain orientation during the prograde metamorphism, but mostly it can form as newly crystallized crystals from water-rich solutions replacing earlier minerals such as garnets or micas and filling veins during the retrograde metamorphism (Kryza et al. \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e1990\u003c/span\u003e). The occurrence of stilpnomelane was reported from Čučma \u0026ndash; Čierna baňa manganese deposit associated with kutnohorite-ankerite-quartz veins (Faryad \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e1994\u003c/span\u003e; Peterec \u0026amp; Ďuďa \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2003\u003c/span\u003e). Stilpnomelane in the studied metacarbonates based on mutual relationship with spessartine appears to be a younger mineral formed by partial dissolution and replacement of spessartine generated as a recrystallization product along the consumed spessartine outer cores (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb). These textures strongly indicate lower greenschist facies conditions, aligning with the previous calculated results.\u003c/p\u003e \u003cp\u003eStilpnomelane contains significant Mn (up to 2.32 \u003cem\u003eapfu\u003c/em\u003e), suggesting substitution with its Mn-analogue franklinphilite K\u003csub\u003e4\u003c/sub\u003eMn\u003csub\u003e48\u003c/sub\u003e(Si,Al)\u003csub\u003e72\u003c/sub\u003e(O,OH)\u003csub\u003e216\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO) (Dunn et al. \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e1992\u003c/span\u003e), and Mg (up to 1.68 \u003cem\u003eapfu\u003c/em\u003e), indicating a further solid solution with its Mg-analogue lennilenapeite (K\u003csub\u003e6\u0026thinsp;\u0026minus;\u0026thinsp;7\u003c/sub\u003eMg\u003csub\u003e48\u003c/sub\u003e(Si,Al)\u003csub\u003e72\u003c/sub\u003e(O,OH)\u003csub\u003e216\u003c/sub\u003e\u0026middot;16H\u003csub\u003e2\u003c/sub\u003eO (Dunn et al. \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e1984\u003c/span\u003e), reflecting the extensive compositional variations within these isostructural stilpnomelane group phases. Total alkali content in studied mineral remains low (\u0026lt;\u0026thinsp;0.5 \u003cem\u003eapfu;\u003c/em\u003e Tab. S1), likely due to limited supply of K and Na from the surrounding environment. The deficit is therefore partially balanced by a relatively increased content of Ca, influenced by an abundant presence of Mn-rich calcite and spessartine in the host rocks.\u003c/p\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003eMineral composition and multistage development of manganese mineralization\u003c/h2\u003e \u003cp\u003eThe formation of manganese mineralization at the studied locality was probably caused by the transport of primary manganese oxides in higher oxidation states (Mn\u003csup\u003e3+\u003c/sup\u003e/Mn\u003csup\u003e4+\u003c/sup\u003e) to a shallower-water sedimentary environment rich in organic matter. These conditions created anaerobic, CO\u003csub\u003e2\u003c/sub\u003e-rich and reduced conditions that led the crystallization of Mn\u003csup\u003e2+\u003c/sup\u003e carbonates, primarily rhodochrosite. (Brusnitsyn \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2007\u003c/span\u003e; Johnson et al. \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). Further formation of Mn-rich silicates was influenced by quartz- and clay-rich protolith providing Si, Al, Fe, Mg and other components, necessary for crystallization of silicates produced by continuous increase in metamorphic conditions during the prograde Variscan metamorphic event.\u003c/p\u003e \u003cp\u003eRhodonite remains stable under low-pressure and low-temperature conditions, transformation to a higher pressure/temperature pyroxmangite-type structure was experimentally calculated at 300 MPa pressure and temperatures around 350\u0026ndash;400\u0026ordm;C (Maresch \u0026amp; Mottana \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e1976\u003c/span\u003e). Additionally, the incorporation of Ca stabilizes the rhodonite-type structure, while Fe\u003csup\u003e2+\u003c/sup\u003e and Mg\u003csup\u003e2+\u003c/sup\u003e further influences stability field towards pyroxmangite-type structure (Jim\u0026eacute;nez-Mil\u0026aacute;n \u0026amp; Velilla 1998). Based on PXRD data (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) and the Ca, Mg and Fe\u003csup\u003e2+\u003c/sup\u003e contents (Tab. S1), along with the suitable metamorphic conditions, a rhodonite-type structure is preserved in the studied rhodonite group minerals. Rhodonite group minerals have increased content of FeO (5.7\u0026ndash;10.5 wt.%; Tab. S1), what causes Fe as dominant cation at the position \u003cem\u003eM\u003c/em\u003e4, leaning to the ferrorhodonite composition (Shchipalkina et al. \u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). Increased content of FeO (up to 7.1 wt.%) in rhodonites was as well observed by Rojkovič (\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2000\u003c/span\u003e). Similarly, tephroite forms in the greenschist facies conditions below 420\u0026ordm;C at low \u003cem\u003eX\u003c/em\u003e\u003csub\u003e\u003cem\u003eCO2\u003c/em\u003e\u003c/sub\u003e (\u0026lt;\u0026thinsp;0.2) (Peters et al. \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e1973\u003c/span\u003e) at the expense of rhodochrosite and quartz assemblages (Mohapatra \u0026amp; Nayak 2003). Slightly increased fayalite molecule (8.7 mol.%) is also observed associating with Fe-rich rhodonite, however, inclusions in spessartine contain tephroite with significantly increased fayalite molecule (up to 31 mol.%) (Tab. S1). The absence of rhodonite inclusions in spessartine might be explained due to the absence of pyroxenoids in former association, consequently incorporating Fe in tephroite in the Fe-enriched system in the protolith environment. The presence of magnetite, Fe-rich rhodonite and tephroite permits the greater Fe entry into the coexisting spessartine (up to 17.2 mol. % Adr). Spessartine forms during the early low-pressure stages of prograde metamorphism, with stability field at approximately 300\u0026ordm;C (Theye et al. \u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e1996\u003c/span\u003e). Spessartine incorporations consisting of quartz, magnetite, pyrophanite, pyrosmalite-(Mn), tephroite and rhodochrosite might represent a residual phases (Nyame \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2001\u003c/span\u003e) of pre-Alpine manganese assemblages. The high content of Fe in these minerals indicates the simultaneous formation of manganese mineralization and nearby magnetite lens and further supports similar characteristics observed in the formation of magnetite lenses associated with manganese ore at the Prakovce \u0026ndash; Zimn\u0026aacute; Voda occurrence (Myšľan et al. \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2024a\u003c/span\u003e) and the abundant magnetite impregnations found in the oldest Mn assemblage at the Beltiar \u0026ndash; J\u0026uacute;lius locality (Myšľan et al. \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). Pyrosmalite-(Mn) was generated via hydration and chlorination processes of the Mn-rich silicates (Stillwell \u0026amp; McAndrew \u003cspan citationid=\"CR63\" class=\"CitationRef\"\u003e1957\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eFurther development of carbonate-silicate manganese mineralization at the Smoln\u0026iacute;k - Mal\u0026aacute; Hekerov\u0026aacute; deposit was during the Alpine stage of metamorphism significantly influenced by tectono-metamorphic deformation forming the cracks and fissures and subsequent recrystallization and precipitation of newly formed mineral assemblages incorporated mostly in the form of veins. Veins are dominantly filled with quartz, slightly Fe-enriched rhodochrosite, kutnohorite and Fe-poor rhodonite. Rhodonite is often overgrown by caryopilite (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ef) or greenalite, which is formed as a retrograde product during the greenschist metamorphism by alteration of anhydrous Si-rich phases (Abrecht \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1989\u003c/span\u003e). These phyllosilicates also occur in veins. Slightly increased content of Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e in caryopilite (up to 0.08 \u003cem\u003eapfu\u003c/em\u003e) suggests its syngenetical formation with a vein-type pyrosmalite-(Mn) enriched in Fe (up to 2.97 \u003cem\u003eapfu\u003c/em\u003e) during the infiltration or remobilization of H\u003csub\u003e2\u003c/sub\u003eO and Cl-rich fluids. Clinochlore-chamosite chlorites with increased pennantite molecule (up to 0.76 \u003cem\u003eapfu\u003c/em\u003e) (Tab. S1) occur in veins, locally partially replacing spessartine (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eg), suggesting their retrograde formation. Changes in Fe content in minerals reflects its mobility during the Alpine metamorphic development, where Fe was released from the primary phases and subsequently incorporated to the newly generated or recrystallized minerals.\u003c/p\u003e \u003cp\u003eAmphiboles were observed mostly in the veins, locally forming a massive aggregates with strong zoning. The stability of Mg-Fe-Mn amphiboles depends on the Mn/(Mn\u0026thinsp;+\u0026thinsp;Mg) ratio. The lower stability limit of clino-suenoite was established at the temperature around 400\u0026ordm;C and 200 MPa pressure, which might be influenced by iron content reducing its stability limits (Melcher \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e1995\u003c/span\u003e). Association of present amphiboles is not common, they were identified only at a few localities, such as the Pb-Zn skarn deposits in Madan, Bulgaria, where they formed through hydrothermal alteration and replacement of early Mn-rich pyroxenes (Vassileva \u0026amp; Bonev \u003cspan citationid=\"CR68\" class=\"CitationRef\"\u003e2001\u003c/span\u003e). Studied clino-suenoite and clino-ferro-suenoite appear to replace actinolite (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ee) while maintaining its original shape. The replacement involves cation exchange, with removal of Ca\u003csup\u003e2+\u003c/sup\u003e and incorporation of Mn\u003csup\u003e2+\u003c/sup\u003e gradually replaced by Mg\u003csup\u003e2+\u003c/sup\u003e and Fe\u003csup\u003e2+\u003c/sup\u003e. These processes depend on metamorphic pT conditions as well as low to moderate oxygen fugacity (\u003cem\u003ef\u003c/em\u003eO\u003csub\u003e2\u003c/sub\u003e), which stabilizes Mn\u003csup\u003e2+\u003c/sup\u003e within the silicate structure (Brusnitsyn \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2007\u003c/span\u003e; Kanungo et al. \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). The formation of a clino-ferro-suenoite rim around clino-suenoite aligns with increased Fe mobility and its incorporation into later minerals during the Alpine metamorphic stage. The compositional and textural changes in manganese ore during the metamorphic evolution can be best observed at spessartine garnets (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec-f). The central part of garnets (Sps1) consists of relatively stable and homogenous mass, interrupted only with small cracks. The formation of this garnet is consistent with the processes taking place during the prograde stage of metamorphism discussed above. The outer part of garnet (Sps2) shows increased porosity and a change in chemical composition, with decreased Mn (up to 73.3 mol.% Sps2) and increased Fe (up to 37.2 mol.% Adr; up to 0.3 mol.% Alm) contents compared to sps1. This change is likely caused by the partial dissolution of garnet outer parts accompanied by release of Mn and/or incorporation of Fe-rich fluids during the retrograde phase along the garnet outer boundary. The third stage is characteristic by enrichment of CO\u003csub\u003e2\u003c/sub\u003e and Ca in metamorphic environment, resulting in crystallization of thin calcite zone, separating the third spessartine generation (Sps3). This spessartine forms homogenous rims around pre-existing minerals, enriched in Fe (up to 32.9 mol.% Adr; up to 9.5 mol. Alm) and decreased in Mn (up to 78.1 mol.% Sps3). The Sps1 and Sps2 garnets are locally completely dissolved, resulting in elements release to the system with concurrent incorporation of Fe-rich fluids generating the zones of Sps3 garnet. Significance of fluid infiltration during the formation of new generation of garnets has been proved by various authors (Konrade-Smolke et al. 2007; Faryad et al. \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2010\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eRarely alabandite occurs associated with rhodochrosite, it has been suggested to be temperature dependant phase, manifested by an increase in Fe content (Skinner \u0026amp; Luce \u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e1971\u003c/span\u003e), and FeS activity (Fukuoka \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e1981\u003c/span\u003e). Alabandite remains stable within the stability field of iron, pyrrhotite and pyrite under consistently reduced conditions (Cabral et al. \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2019\u003c/span\u003e), stability field expands with increasing temperature (Holland \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e1959\u003c/span\u003e). However, increased content of Fe in alabandite cannot be clearly ruled out to be caused by pyrrhotite inclusions (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea).\u003c/p\u003e \u003cp\u003eSulfidic mineralization bound to the manganese carbonate-silicate ore at the Smoln\u0026iacute;k \u0026ndash; Mal\u0026aacute; Hekerov\u0026aacute; deposit likely formed from hydrothermal fluids linked to Alpine tectono-metamorphic evolution. Their presence in cavities and veins suggests its late formation. Unlike other deposits in the Spišsko-gemersk\u0026eacute; rudohorie Mts., there is no significant enrichment in Co or Ni, however it displays one of the biggest accumulation of these phases in the area of study interest. High incorporation of these phases to the manganese ore was observed, though Mn enrichment in sulfides remains minimal (up to 0.02 \u003cem\u003eapfu\u003c/em\u003e; Tab. S1). This high sulfides concentration may be attributed to the surrounding lithology, such as metalydites and graphitic phyllites, which provided the necessary sources of sulphur and other elements during the Alpine metamorphic stage.\u003c/p\u003e \u003cp\u003eThe last stage of manganese ore evolution is characterised by formation of supergene zone, which is not part of this study, however Rojkovič (\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2000\u003c/span\u003e, \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2001\u003c/span\u003e) identified pyrolusite, todorokite, cryptomelane, goethite and \u003cem\u003elimonite\u003c/em\u003e as oxidation products of primary mineral association.\u003c/p\u003e \u003c/div\u003e"},{"header":"Conclusions","content":"\u003cp\u003eA polygenetic mineral assemblage of metamorphosed carbonate-silicate manganese ore at the Smoln\u0026iacute;k \u0026ndash; Mal\u0026aacute; Hekerov\u0026aacute; deposit is closely related with metacarbonate bodies hosted in lydites, quartz-muscovitic and graphite-muscovitivic phyllites of metavolcano-sedimentary sequences of the Bystr\u0026yacute; potok Formation (Gelnica Group). Mineralization in associating metacarbonate bodies shows huge variety of phases, identified as calcite (locally enriched in Mn), spessartine, stilpnomelane, titanite, fluorapatite and pyrite, suggesting to a certain content manganese incorporation to the precursor carbonate sedimentary environment. Spessartine and titanite are formed during the prograde stage of Variscan metamorphic development at the temperatures as low as ~\u0026thinsp;300\u0026ordm;C. Stilpnomelane was formed through mineral replacement of spessartine, aligning with lower greenschist facies conditions. Stilpnomelane exhibits compositional variation due to Mn and Mg substitution and increased Ca component in mineral structure, reflecting the chemical composition of host rocks.\u003c/p\u003e \u003cp\u003eThe manganese carbonate-silicate ore contains Variscan and Alpine mineral assemblages consisting of rhodochrosite, kutnohorite, rhodonite-ferrorhodonite series, spessartine, tephroite, pyrosmalite-(Mn), magnetite, pyrophanite, clino-suenoite, clino-ferro-suenoite, actinolite, caryopilite, greenalite, chamosite, clinochlore, quartz, alabandite and sulfidic mineralization identified as pyrite, pyrrhotite, galena, sphalerite and chalcopyrite. The first generated mineral assemblage developed during the prograde metamorphism in greenschist facies condition, later processes led to the deformation and vein formation with subsequent filling of younger generation of mineral assemblages, alongside with infiltration of Fe-rich fluids, alteration of Si-rich phases, recrystallization and retrograde metamorphism. Compositional and textural changes in manganese ore are most evident in spessartine garnets, where the core (Sps1) remains stable with high Mn content (up to 89.4 mol.% Sps), while the outer zone (Sps2) shows increased porosity, decreased Mn (73.3 mol.% Sps) and elevated Fe (37.2 mol.% Adr) due to fluid interaction during retrograde metamorphism. A third spessartine generation (Sps3) formed as Fe-rich fluids infiltrated, leading to crystallization of new spessartine zone. Sulfidic mineralization in manganese ore likely resulted from hydrothermal fluids during Alpine tectono-metamorphic evolution, with high sulfide concentrations in manganese ore.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eConceptualization: [P.M., M.Š.], Methodology: [P.M., J.S., T.M.], Figures: [P.M., J.S.], Writing - original draft preparation: [P.M., M.Š., J.S., P.R.].\u003c/p\u003e\u003ch2\u003eAcknowledgement:\u003c/h2\u003e \u003cp\u003eThe authors are thankful to handling editor XY as well as reviewers XY1 and XY2 and for their suggestions. We also want to thank B. Volekov\u0026aacute; for Raman spectroscopy. This study was financially supported by APVV-22-0041, VEGA 2/0029/23 and DKRVO 2024\u0026ndash;2028/1.II.a, 00023272 projects.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eAbrecht J (1989) Manganiferous phyllosilicate assemblages: occurrences, compositions and phase relations in metamorphosed Mn deposits. Contrib Mineral Petr 103:228\u0026ndash;241\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBajan\u0026iacute;k Š, Voz\u0026aacute;rov\u0026aacute; A, Hanzel V, Ivanička J, Mello J, Pristaš J, Reichwalder P, Snopko L, Voz\u0026aacute;r J (1983) Explanations to geological map of the Slovensk\u0026eacute; Rudohorie Mts.- Eastern part, 1:50 000. ŠG\u0026Uacute;DŠ, Bratislava 1\u0026ndash;223 (in Slovak)\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBrusnitsyn AI (2007) Association of Mn-bearing minerals as indicators of oxygen fugacity during the metamorphism of metalliferous deposits. 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Acta mineral-petrograp 41:102\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSpišiak J, Hovorka D, Rybka R, Turan J (1989) Spessartine and piemontite in Lower Paleozoic metasediments of the Inner West Carpathians. Čas Mineral Geol 34:17\u0026ndash;30 (in Slovak)\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eStillwell FL, McAndrew J (1957) Pyrosmalite in the Broken Hill lode, New South Wales. Mineral Mag 31:371\u0026ndash;380\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eŠtevko M, Myšľan P, Biagioni C, Mauro D, Mikuš T (2023) Ferriandrosite-(Ce), a new member of the epidote supergroup from Betliar, Slovakia. Mineral Mag 87:887\u0026ndash;895\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eŠtevko M, Plech\u0026aacute;ček J, Vencl\u0026iacute;k V, Mal\u0026iacute;kov\u0026aacute; R (2015) Hausmannite a manganosite from the Čučma-Čierna baňa manganese deposit (Slovak Republic). 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Z\u0026aacute;p Karp ser mineral. petrog geoch metalog 16:55\u0026ndash;117 (in Slovak)\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eVoz\u0026aacute;rov\u0026aacute; A, Ivanička J (1993) Litogeochemistry of Early Paleozoic metasediments in the Southern Gemericum. Z\u0026aacute;p Karp, ser mineral. petrog geoch metalog 16:119\u0026ndash;146 (in Slovak)\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eVoz\u0026aacute;rov\u0026aacute; A, Konečn\u0026yacute; P, Šarinov\u0026aacute; K, Voz\u0026aacute;r J (2014) Ordovician and Cretaceous tectonothermal history of the Southern Gemericum Unit from microprobe monazite geochronology (Western Carpathians, Slovakia). 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J Appl Cryst 10:73\u0026ndash;74\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"mineralogy-and-petrology","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"mipe","sideBox":"Learn more about [Mineralogy and Petrology](http://link.springer.com/journal/710)","snPcode":"710","submissionUrl":"https://submission.nature.com/new-submission/710/3","title":"Mineralogy and Petrology","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Spišsko-gemerské rudohorie Mts., Smolník, manganese mineralization, metacarbonates, rhodonite, spessartine, stilpnomelane","lastPublishedDoi":"10.21203/rs.3.rs-6072303/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6072303/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eMetamorphic manganese mineralization recently studied at the Smoln\u0026iacute;k \u0026ndash; Mal\u0026aacute; Hekerov\u0026aacute; deposit is located within the Early Paleozoic metamorphic volcano-sedimentary sequences of the Bystr\u0026yacute; potok Formation, Gelnica Group of the Gemeric Unit, in the Spišsko-gemersk\u0026eacute; rudohorie Mountains, eastern Slovakia. The manganese mineralization is closely associated with metacarbonate bodies, where Mn-rich calcite, spessartine, titanite, stilpnomelane, fluorapatite and pyrite have been identified. Stilpnomelane contains increased Mn (up to 2.32 \u003cem\u003eapfu\u003c/em\u003e) and Mg (up to 1.68 \u003cem\u003eapfu\u003c/em\u003e), while being depleted in Ca, K, Ba and Na. Stilpnomelane is considered a retrograde phase, formed by the partial dissolution of spessartine under the lower greenschist facies conditions. The carbonate-silicate bodies of manganese mineralization consist of rhodochrosite, kutnohorite, calcite, rhodonite group minerals, spessartine, tephroite, pyrosmalite-(Mn), magnetite, pyrophanite, clino-suenoite, clino-ferro-suenoite, actinolite, clinochlore, chamosite, caryopilite, greenalite, quartz, alabandite, pyrite, pyrrhotite, galena, sphalerite and chalcopyrite. This manganese assemblage is a result of multistage metamorphism during the Variscan and Alpine tectono-metamorphic evolution, resulting in characteristic mineral assemblages influenced by release or incorporation of Fe-enriched fluids, alteration of silicates and recrystallization of newly generated phases. Polycyclic development is most evident in spessartine crystals, which display chemically distinguishable zones reflecting the multi-stage metamorphic development of manganese mineralization. The presence of significantly Fe-rich tephroite (up to 31 mol.% fayalite), pyrosmalite-(Mn) (up to 2.39 \u003cem\u003eapfu\u003c/em\u003e Fe), magnetite, pyrophanite, rhodochrosite and quartz inclusions considered as residual phases in spessartine preserves the primary chemical composition of the later developing manganese ore. This suggests its concurrent forming with nearby magnetite lenses, as well as observed at the other Western Carpathian occurrences. Post-Variscan hydrothermal activity, influenced by suitable host rocks, led to the larger accumulation of sulfides in low-pressure and low-temperature metamorphic manganese occurrences in the Western Carpathians.\u003c/p\u003e","manuscriptTitle":"Metamorphic manganese mineralization bound to the metacarbonate lenses at the Smolník – Malá Hekerová deposit in the Spišsko-gemerské rudohorie Mts., Western Carpathians (Slovakia)","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-02-26 09:15:37","doi":"10.21203/rs.3.rs-6072303/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-03-16T15:01:34+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-03-06T18:26:41+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"52657811046578764588770285017681400783","date":"2025-03-02T18:10:19+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-02-28T00:16:40+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-02-24T15:05:06+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-02-24T09:11:50+00:00","index":"","fulltext":""},{"type":"submitted","content":"Mineralogy and Petrology","date":"2025-02-20T13:16:32+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"mineralogy-and-petrology","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"mipe","sideBox":"Learn more about [Mineralogy and Petrology](http://link.springer.com/journal/710)","snPcode":"710","submissionUrl":"https://submission.nature.com/new-submission/710/3","title":"Mineralogy and Petrology","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"47a5b26d-0ddc-4a8d-86e9-c4dd6e9c52c4","owner":[],"postedDate":"February 26th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-06-09T16:10:10+00:00","versionOfRecord":{"articleIdentity":"rs-6072303","link":"https://doi.org/10.1007/s00710-025-00922-4","journal":{"identity":"mineralogy-and-petrology","isVorOnly":false,"title":"Mineralogy and Petrology"},"publishedOn":"2025-06-03 15:57:38","publishedOnDateReadable":"June 3rd, 2025"},"versionCreatedAt":"2025-02-26 09:15:37","video":"","vorDoi":"10.1007/s00710-025-00922-4","vorDoiUrl":"https://doi.org/10.1007/s00710-025-00922-4","workflowStages":[]},"version":"v1","identity":"rs-6072303","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6072303","identity":"rs-6072303","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}