Study on the Properties of Waste Apatite Phosphogypsum as a Raw Material of Prospective Applications

Waste and Biomass Valorization, Vol. 0, iss. 0 (2018) (online first)This paper presents the results of the study on chemical and the physical properties of waste phosphogypsum (PG) of apatite origin from the former chemical plant Wizow, Poland which are important for further processing and economic use. The research was carried out to verify whether the waste might be useful as a raw material for rare earth elements (REE) recovery and the manufacture of building materials. The following methods were chosen: X-ray diffraction, scanning electron microscopy with an energy-dispersive X-ray detector, atomic absorption spectrometry, inductively coupled plasma spectrometry, differential thermal analysis, thermogravimetry, and gamma spectrometry with natural radioactive contamination analyzer. It has been proven that the chemical physical properties of phosphogypsum provide an opportunity to utilize this waste material as a source of REE and raw material for building purposes. PG contains an overall amount of REE in the interval of 0.343–0.637% by mass and does not show radioactivity level which would exclude it from construction purposes. The presented results serve as the basis for currently available technological directions in the management of apatite PG for useful trade products, which creates a chance for the elimination of its storage necessity by further processing

Crystal Chemistry of an Erythrite-Köttigite Solid Solution (Co3–xZnx) (AsO4)2·8H2O

A wide compositional range, covering about 90% of an expected erythrite-köttigite substitutional solid solution with extreme compositions of (Co2.84Mg0.14Zn0.02) (AsO4)2·8H2O and (Zn2.74Co0.27) (AsO4)2·8H2O, was revealed in a suite of samples from a polymetallic ore deposit in Miedzianka, SW Poland. Members of the solid solution series were examined by means of Electron Probe Microanalysis (EPMA), Scanning Electron Microscopy (SEM)/Energy-Dispersive Spectrometer (EDS), X-ray single-crystal and powder diffraction, and Raman spectroscopy. Metal cations were randomly distributed between two special octahedral sites in the erythrite–köttigite structure. In response to Co ↔ Zn substitutions, small but significant changes in bond distances (particularly in [AsO4] tetrahedra), rotation, and distortion of co-ordination polyhedra were observed. Two sub-series of dominant cationic substitutions (Co-Mg-Ni and Co-Fe-Zn) were noted within the arsenate series of vivianite-group minerals linked by erythrite. The paragenetic sequence erythrite → Zn-rich erythrite → Co-rich köttigite → köttigite reflects the evolution of the solution’s pH towards increased acidity and a relative increase in the concentration of Zn ions following precipitation of erythrite

Third Worldwide Occurrence of Juangodoyite, Na2Cu(CO3)2, and Other Secondary Na, Cu, Mg, and Ca Minerals in the Fore-Sudetic Monocline (Lower Silesia, SW Poland)

Na-Cu carbonates are relatively rare secondary minerals in weathering zones of ore deposits. Hereby we describe mineral composition and crystal chemistry of the most important secondary (Na)Cu minerals and their Na- and Mg-bearing associates forming rich paragenesis in Rudna IX mine. A non-bulky Ca-rich dripstone-like paragenesis from Lubin Główny mine is also characterized, using Powder X-Ray Di raction, Rietveld, and Electron Microprobe methods. Light blue juangodoyite (3rd occurrence worldwide) and darker chalconatronite are the most important members of the Rudna IX paragenesis, being associated with malachite, aragonite (intergrown with hydromagnesite and northupite), and probably cornwallite. Most of the minerals are chemically close to their ideal composition, with minor Mg substitution in malachite. Cu chlorides are mainly represented by clinoatacamite and probably herbertsmithite. Additional, minor phases include trace Cu minerals langite, wroewolfeite, and a lavendulan-group mineral, and monohydrocalcite. Separate halite-rich encrustations are shown to be filled with eriochalcite, ktenasite, and kröhnkite. The most likely to be confirmed coexisting species include paratacamite, wooldridgeite/nesquehonite, johillerite, melanothallite, and kipushite. The Lubin paragenesis mainly comprises aragonite, gypsum, rapidcreekite, and monohydrocalcite, with trace vaterite. Blue colouration is mainly provided by a yet unspecified Ni-, Co-, Mg-, and Mn-bearing Cu-Zn-Ca arsenate mineral close to parnauite

Towards Zn-dominant tourmaline: A case of Zn-rich fluor-elbaite and elbaite from the julianna system at Piława Górna, Lower Silesia, SW Poland

Tourmalines are a group of minerals which may concentrate various accessory components, e.g., Cu, Ni, Zn, Bi, Ti, and Sn. The paper presents fluor-elbaite and elbaite from a dyke of the Julianna pegmatitic system at Piława Górna, at the NE margin of the Bohemian Massif, SW Poland, containing up to 6.32 and 7.37 wt % ZnO, respectively. Such high amounts of ZnO are almost two times higher than in the second most Zn-enriched tourmaline known to date. The compositions of the Zn-rich tourmalines from Piława Górna, studied by electron micropropy and Raman spectroscopy, correspond to the formulae:X(Na0.733Ca0.013□0.254)Y Σ1 (Al1.033Li0.792 Zn0.755Fe2+0.326Mn0.094)Z Σ3 Al6(TSi6O18)(BO3)V 3 (OH)W 3 (F0.654OH0.344), andX(Na0.779Ca0.015□0.206)Σ1 Y(Al1.061Li0.869Zn0.880Fe2+0.098Mn0.094)Z Σ3 Al6(TSi6O18)(BO3)V 3 (OH)W 3 (OH0.837F0.163), respectively, with Zn as one of the main octahedral occupants. A comparison with other tourmalines and associated Zn-rich fluor-elbaite and elbaite from the pegmatite indicates that atypically high Zn-enrichment is not a result of Zn-Fe fractionation, but dissolution and reprecipitation induced by a late (Na,Li,B,F)-bearing fluid within the assemblage of gahnite spinel and primary schorl-type tourmaline. This strongly suggests Na-Li-B-F metasomatism of gahnite-bearing mineral assemblages as that is the only environment that can promote crystallization of a hypothetical Zn-dominant tourmaline. The compositions of the Zn-rich fluor-elbaite and elbaite suggest three possible end-members for such a hypothetical tourmaline species: NaZn3Al6(Si6O18)(BO3)3(OH)3(OH), □(Zn2Al)Al6(Si6O18)(BO3)3(OH)3(OH) and Na(Zn2Al)Al6(Si6O18)(BO3)3(OH)3O by analogy with other tourmalines with divalent Y occupants, such as schorl/foitite/oxy-schorl and dravite/magnesio-foitite/oxy-dravite.National Centre for Atmospheric Scienc

Chemical composition of Mn-and Cl-rich apatites from the szklary pegmatite, central sudetes, SW Poland: Taxonomic and genetic implications

The research was founded by the National Science Centre (Poland) grant number 2015/17/B/ST10/03231 and the University of Wroclaw grant 0401/0156/18Although calcium phosphates of the apatite group (apatites) with elevated contents of Mn are common accessory minerals in geochemically evolved granitic pegmatites, their Mn-dominant analogues are poorly studied. Pieczkaite,M1 Mn2 M2 Mn3 (PO4)3 X Cl, is an exceptionally rare Mn analogue of chlorapatite known so far from only two occurrences in the world, i.e., granitic pegmatites at Cross Lake, Manitoba, Canada and Szklary, Sudetes, SW Poland. In this study, we present the data on the compositional variation and microtextural relationships of various apatites highly enriched in Mn and Cl from Szklary, with the main focus on compositions approaching or attaining the stoichiometry of pieczkaite (pieczkaite-like apatites). The main goal of this study is to analyze their taxonomical position as well as discuss a possible mode of origin. The results show that pieczkaite-like apatites represent the Mn-rich sector of the solid solutionM1 (Mn,Ca)2 M2 (Mn,Ca)3 (PO4)3 X (Cl,OH). In the case of cation-disordered structure, all these compositions represent extremely Mn-rich hydroxylapatite or pieczkaite. However, for cation-ordered structure, there are also intermediate compositions for which the existence of two hypothetical end-member species can be postulated:M1 Ca2 M2 Mn3 (PO4)3 X Cl andM1 Mn2 M2 Ca3 (PO4)3 X OH. In contrast to hydroxylapatite and pieczkaite, that are members of the apatite-group, the two hypothetical species would classify into the hedyphane group within the apatite supergroup. The pieczkaite-like apatites are followed by highly Mn-enriched fluor-and hydroxylapatites in the crystallization sequence. Mn-poor chlorapatites, on the other hand, document local contamination by the serpentinite wall rocks. We propose that pieczkaite-like apatites in the Szklary pegmatite formed from small-volume droplets of P-rich melt that unmixed from the LCT-type (Li–Cs–Ta) pegmatite-forming melt with high degree of Mn-Fe fractionation. The LCT melt became locally enriched in Cl through in situ contamination by wall rock serpentinites.National Science Centre (Poland), University of Wrocla

Pb-Rich Slags, Minerals, and Pollution Resulted from a Medieval Ag-Pb Smelting and Mining Operation in the Silesian-Cracovian Region (Southern Poland)

Since the 12th century in the Silesian-Cracovian area, lead, litharge, and silver have been produced by the pyrometallurgical processing of Pb-Ag-Zn ore. Slags and soils contaminated with heavy metals (Zn, Pb, Cd, Fe, Mn, As) were the subject of this research. Samples were collected during archaeological works in the area of early medieval metallurgical settlement. The main goals of the analyses (Scanning Electron Miscroscopy-Energy Dispersive Spectroscopy (SEM-EDS), Electron Probe Microanalyzer (EPMA), X-ray di raction (XRD), Atomic Absorption Spectroscopy (AAS)) were the determination of the mineralogical composition of furnace batches and smelting temperatures and conditions. In soils, the anthropogenic phases enriched in Pb, Zn, Fe, Mn, P, and primary minerals like goethite, ferrihydrite, sphalerite, galena, smithsonite, minrecordite, cerussite, gypsum, anglesite, jarosite, and hemimorphite were identified. The soil from former metallurgical settlements contained up to 1106 mg kg1 Pb, 782 mg kg1 Zn, 4.7 mg kg1 Cd in the fine fraction. Much higher heavy metal concentrations were observed in the waste products of ore rinsing, up to 49,282 mg kg1 Pb, 64,408 mg kg1 Zn, and 287 mg kg1 Cd. The medieval smelting industry and Pb-Ag-Zn ore processing are marked by highly anomalous geochemical pollution (Pb, Zn, Cd, Fe, Mn, Ba) in the topsoil. The methods of mineralogical investigation, such as SEM-EDS or EMPA, can be used to identify mineralogical phases formed during metallurgical processes or ore processing. Based on these methods, the characteristic primary assemblage and synthetic phases were identified in the area polluted by medieval metallurgy and mining of Pb-Ag-Zn ores, including MVT (Mississippi Valley Type) deposits. The minerals distinguished in slags and the structural features of metal-bearing aggregates allow us to conclude that batches have included mostly oxidised minerals (PbCO3, ZnCO3, CaZn(CO3)2, FeOOH), sulfides (PbS and ZnS) and quartz (SiO2). The laboratory experiment of high-temperature heating of the examined slags showed that smelting temperatures used in the second half of 13th century were very high and could have reached up to 1550 C. The results indicate, that geochemical and mineralogical methods can be used to obtain important information from archaeological sites, even after archaeological work has long ceased

Żabińskiite, ideally Ca(Al_(0.5)Ta_(0.5))(SiO_4)O, a new mineral of the titanite group from the Piława Górna pegmatite, the Góry Sowie Block, southwestern Poland

Żabińskiite, ideally Ca(Al_(0.5)Ta_(0.5))(SiO_4)O, was found in a Variscan granitic pegmatite at Piława Górna, Lower Silesia, SW Poland. The mineral occurs along with (Al,Ta,Nb)- and (Al,F)-bearing titanites, a pyrochlore-supergroup mineral and a K-mica in compositionally inhomogeneous aggregates, ∼120 μm × 70 μm in size, in a fractured crystal of zircon intergrown with polycrase-(Y) and euxenite-(Y). Żabińskiite is transparent, brittle, brownish, with a white streak, vitreous lustre and a Mohs hardness of ∼5. The calculated density for the refined crystal is equal to 3.897 g cm^(–3), but depends strongly on composition. The mineral is non-pleochroic, biaxial (–), with mean refractive indices ≥1.89. The (Al,Ta,Nb)-richest żabińskiite crystal, (Ca_(0.980)Na_(0.015))Σ=0.995(Al_(0.340) Fe^(3+)_(0.029) Ti_(0.298)V_(0.001)Zr_(0.001)Sn_(0.005)Ta_(0.251)Nb_(0.081))Σ=1.005[(Si_(0.988)Al_0.012)O_(4.946)F_(0.047)(OH)_(0.007))Σ=5.000]; 60.7 mol.% Ca[Al_(0.5)(Ta,Nb)_(0.5)](SiO_4)O; is close in composition to previously described synthetic material. Żabińskiite is triclinic (space group symmetry Ai and has unit-cell parameters a = 7.031(2) Å, b = 8.692(2) Å, c = 6.561(2) Å, α = 89.712(11)°, β = 113.830(13)°, γ = 90.352(12)° and V = 366.77 (11) Å3. It is isostructural with triclinic titanite and bond-topologically identical with titanite and other minerals of the titanite group. Żabińskiite crystallized along with (Al,Ta,Nb)-bearing titanites at increasing Ti and Nb, and decreasing Ta activities, almost coevally with polycrase-(Y) and euxenite-(Y) from Ca-contaminated fluxed melts or early hydrothermal fluids