Alunogen from the sulfate efflorescence of the Stone Town Nature Reserve in Ciężkowice (the Outer Carpathian Mountains, Poland)

Alunogen (Al2(SO4)3∙17H2O), a rare secondary mineral, has been found in the efflorescence on sandstones from the Stone Town Nature Reserve in Ciężkowice, southeastern Poland. This is probably the first find of this salt on such rocks in Poland. Alunogen forms in various geological environments, but mainly from the oxidation of pyrite and other metal sulfides in ore deposits and Al-rich Earth materials under low-pH conditions. Its crystallization at this particular site depends on a set of necessary physicochemical (pH, concentration), climatic (season, temperature, humidity), site-related (location and protection of efflorescence), and mineralogical (the presence of pyrite) conditions. This paper presents the mineralogical and geochemical characteristics of the alunogen from the Stone Town Nature Reserve (based on SEM-EDS, XRPD, EPMA and Raman spectroscopy methods) as well as of the efflorescence itself (based on XRPD and STA coupled with QMS and FTIR for the analysis of gas products). Crystals of alunogen take the shape of flakes, often with a hexagonal outline, clustered in aggregates forming a cellular network. Its calculated formula is (Al1.96Fe3+0.01)Σ1.97(SO4)3∙17H2O (based on 12 O and 17 H2O). The unit-cell parameters refined for the triclinic space group P1 are: a = 7.423 (1) Å, b = 26.913 (5) Å, c = 6.056 (1) Å, a = 89.974 (23)°, b = 97.560 (25)°, g = 91.910 (22)°. The Raman spectra (SO4) bands are: intensive 995 cm−1 (ν1); low-intensive 1069, 1093 and 1127 cm−1 (ν3); low-intensive 419 and 443; medium-intensive 470 cm−1 (ν2); and medium-intensive 616 cm−1 (ν4). Those at 530, 312 and at 338 cm−1 are assigned to water vibrations and those at 135, 156, 180 cm−1 to the lattice modes. Although the efflorescence contained an admixture of other minerals (pickeringite, gypsum and quartz), the predominant alunogen is almost chemically pure and the above parameters are consistent with the values reported in the literature for alunogen from different locations and of various origins.

Black "marble" in the Polish architecture - characteristics and possibility of its provenance determination: the case of the Dębnik limestone

Black limestone, also known as black "marble", was widely used in the Polish small-scale architecture and art of the 17th and 18th centuries. Besides the Devonian limestone from Dębnik near Krakow, also popular were the Netherlandish (Wallonian), Devonian to Carboniferous limestones from the Meuse River and Schelde River valleys. This paper deals with the possibility of identifying the rocks imported to Poland. Macroscopic similarities between the Netherlandish rocks and some Dębnik limestones have been highlighted for the oldest Carmelite quarry in Dębnik, exploiting the best stones. The analyses include: optical microscopy, scanning electron microscopy with EDS, X-ray diffraction, X-ray fluorescence and isotope ratio mass spectrometry (13 C and 18 O stable isotopes). Carboniferous limestones from Netherlands can be identified within and distinguished from the Dębnik limestone in the macroscopic observations. Differences, depending on the varieties, are associated primarily with the presence of white calcite fragments of fossils, calcite veins intersecting the rock in all directions or hardness of the limestones. Deeply black Devonian limestones from Wallonia and Dębnik without macrofossils and calcite veins differ in microscopic observations considering their texture, type of microfossils and inventory of non-carbonate components. The characteristic graying and whitening of the black limestones has also been discussed as a possible feature of rock provenance

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

Przeobrażenia amfiboli w porfirach ryodacytowych z Zalasu koło Krakowa Alteration of amphiboles in ryodacitic porphyries from Zalas near Kraków (S Poland) /

Tyt. z nagłówka.Bibliografia s. 166.Dostępny również w formie drukowanej.ABSTRACT: The study was aimed at alteration of amphibole phenocrysts in the porphyries from Zalas. The alteration processes took place at the magmatic stage: development of orthopyroxenes and biotitization, and at the postmagmatic one: chloritization followed by argillitization and formation of feldspars, carbonate minerals, quartz, ilmenite, magnetite and hematite. Post-magmatic alteration resulted from hydrothermal processes of the metasomatic character. KEYWORDS: Zalas, porphyries, amphiboles, pseudomorphs, metasomatic alterations. SŁOWA KLUCZOWE: Zalas, porfiry, amfibole, pseudomorfozy, metasomatoza

Black "marble" in the Polish architecture - characteristics and possibility of its provenance determination: the case of the Dębnik limestone

Tyt. z nagłówka.Bibliogr. s. 203-205.Black limestone, also known as black "marble", was widely used in the Polish small-scale architecture and art of the 17th and 18th centuries. Besides the Devonian limestone from Dębnik near Krakow, also popular were the Netherlandish (Wallonian), Devonian to Carboniferous limestones from the Meuse River and Schelde River valleys. This paper deals with the possibility of identifying the rocks imported to Poland. Macroscopic similarities between the Netherlandish rocks and some Dębnik limestones have been highlighted for the oldest Carmelite quarry in Dębnik, exploiting the best stones. The analyses include: optical microscopy, scanning electron microscopy with EDS, X-ray diffraction, X-ray fluorescence and isotope ratio mass spectrometry (13 C and 18 O stable isotopes). Carboniferous limestones from Netherlands can be identified within and distinguished from the Dębnik limestone in the macroscopic observations. Differences, depending on the varieties, are associated primarily with the presence of white calcite fragments of fossils, calcite veins intersecting the rock in all directions or hardness of the limestones. Deeply black Devonian limestones from Wallonia and Dębnik without macrofossils and calcite veins differ in microscopic observations considering their texture, type of microfossils and inventory of non-carbonate components. The characteristic graying and whitening of the black limestones has also been discussed as a possible feature of rock provenance.Dostępny również w formie drukowanej.KEYWORDS: black limestone, provenance, petrography, stable isotope geochemistry, deterioration, Poland, Belgium

Pickeringite from the Stone Town Nature Reserve in Ciężkowice (the Outer Carpathians, Poland)

Pickeringite, ideally MgAl2(SO4)4·22H2O, is a member of the halotrichite group minerals XAl2(SO4)4·22H2O that form extensive solid solutions along the joints of the X = Fe-Mg-Mn-Zn. The few comprehensive reports on natural halotrichites indicate their genesis to be mainly the low-pH oxidation of pyrite or other sulfides in the Al-rich environments of weathering rock-forming aluminosilicates. Pickeringite discussed here occurs within the efflorescences on sandstones from the Stone Town Nature Reserve in Ciężkowice (the Polish Outer Carpathians), being most probably the first find on such rocks in Poland. This paper presents mineralogical and geochemical characteristics of the pickeringite (based on SEM-EDS, XRPD, EPMA and RS methods) and suggests its possible origin. It belongs to the pickeringite–apjohnite (Mg-Mn joints) series and has the calculated formula Mg0.75Mn0.21Zn0.02Cu0.01Al2.02(S0.99 to 1.00O4)4·22H2O (based on 16O and 22H2O). The unit cell parameters refined for the monoclinic system space group P21/c are: a = 6.1981(28) Å, b= 24.2963(117) Å, c = 21.2517(184) Å and β = 100.304(65)°. The Raman spectra (SO4) bands are the intensive 994 cm−1 and a low-intensive 975 cm−1 (ν1), low-intensive 1081, 1123 and 1145 cm−1 (ν3), 524, 467 and 425cm−1 (ν2), 615 cm−1 (ν4), while those at 344 and 310 cm−1 are attributed to νg H2O and at 223 cm−1 to the lattice modes. Crystallization of pickeringite within the particular tor resulted from a certain set of conditions: climatic (e.g., season, temperature, humidity), physicochemical (e.g., pH, concentration), mineral (the presence of pyrite), and site-related (location and efflorescence protection). The sulfate ions could have been derived from oxidation of pyrite in the Ciężkowice sandstones and possibly are related to local mineral waters

Cement Render and Mortar and Their Damages Due to Salt Crystallization in the Holy Trinity Church, Dominicans Monastery in Cracow, Poland

The investigations focused on the façade of the 17th-century Myszkowskis chapel at the 13th-century Church of the Holy Trinity in Cracow, Poland. Most of the chapel’s façade is made of rusticated limestone blocks, but its lower part is covered with cement render, and the basement consists of irregular pieces of limestone and sandstone, bound and partly replaced with cement mortar. The façade exhibited clearly visible damages: gray soiling of the surface, cracks, scaling, and efflorescence. The study presents characteristics of the cement render and mortar used for stone repair and/or substitution, as well as efflorescence from the lower part of the Myszkowskis chapel façade. The materials were analyzed with optical microscopy, scanning electron microscopy (SEM-EDS), Raman microspectroscopy, X-ray diffractometry (XRPD), and mercury intrusion porosimetry. The analyses demonstrated that the render covering some of the decayed limestone blocks was prepared using Portland cement (residual clinker grains represent alite and belite) as a binding agent, mixed with crushed stone as an aggregate. The cement mortar consisted of rounded quartz grains, rock fragments, and feldspars in very fine-grained masses of calcite and gypsum, also containing relics of cement clinker (alite, belite, ferrite, and aluminate). All these components point out the use of the ordinary Portland cement. Analyses of the efflorescence allowed us to distinguish several secondary salts, among others, thenardite, aphthitalite, and darapskite. The appearance of these phases is related to the composition and physicochemical properties of the building materials, atmospheric alteration agents, air pollution, and some other anthropogenic factors