AGH University of Science and Technology
Mineralogy,Petrography and Geochemistry
This work presents mineralogical and chemical characteristics of weathering crusts developed on sandstones exposed to various air pollution conditions. The samples have been collected from sandstone tors in the Carpathian Foothill and... more
This work presents mineralogical and chemical
characteristics of weathering crusts developed on sandstones
exposed to various air pollution conditions. The samples have
been collected from sandstone tors in the Carpathian Foothill
and from buildings in Kraków. It has been stated that these
crusts differ in both fabric and composition. The sandstone
black crust from tors is rich in organic matter and composed of
amorphous silica. Sulphate incrustations accompanied by dust
particles have been only sometimes observed. Beneath the
black crust, a zone coloured by iron (oxyhydr)oxides occurs.
The enrichment of the surface crust in silica and iron compounds
protects the rock interior from atmospheric impact.
The sandstones from architectonic details are also covered by
a thin carbon-rich black crust, but they are visibly loosened.
Numerous salts, mainly gypsum and halite, crystallise here,
thus enhancing deterioration of the rock. Moreover, spherical
particles originated from industrial emissions are much more
common. Gypsum in natural outcrops, forms isolated and
well-developed crystals, whilst these found on the architectonic
details are finer and densely cover the surface. Such
diversity reflects various concentrations of acid air pollutants
in solutions.
characteristics of weathering crusts developed on sandstones
exposed to various air pollution conditions. The samples have
been collected from sandstone tors in the Carpathian Foothill
and from buildings in Kraków. It has been stated that these
crusts differ in both fabric and composition. The sandstone
black crust from tors is rich in organic matter and composed of
amorphous silica. Sulphate incrustations accompanied by dust
particles have been only sometimes observed. Beneath the
black crust, a zone coloured by iron (oxyhydr)oxides occurs.
The enrichment of the surface crust in silica and iron compounds
protects the rock interior from atmospheric impact.
The sandstones from architectonic details are also covered by
a thin carbon-rich black crust, but they are visibly loosened.
Numerous salts, mainly gypsum and halite, crystallise here,
thus enhancing deterioration of the rock. Moreover, spherical
particles originated from industrial emissions are much more
common. Gypsum in natural outcrops, forms isolated and
well-developed crystals, whilst these found on the architectonic
details are finer and densely cover the surface. Such
diversity reflects various concentrations of acid air pollutants
in solutions.
- by Mariola Marszałek and +1
- •
- Stones Deterioration
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... more
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 (13C and 18O
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.
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 (13C and 18O
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.
The collapsing of the south-east wing of Kapelania at the Św. Józef Church of the Bernardine Convent started in 2010, causing fracturing of the walls around the garden, and especially the cellar rooms under the buildings near the Church.... more
The collapsing of the south-east wing of Kapelania at the Św. Józef Church of the Bernardine Convent started in 2010, causing fracturing of the walls around the garden, and especially
the cellar rooms under the buildings near the Church. The aim of research is to determine the properties and stratigraphy of the earth in the subsoil of the endangered object, as well as of its immediate neighbourhood. Archaeological sources and their interdisciplinary interpretation in the context of the geological profiles conducted, based on the auger holes and narrow open pits, attest to a complex set of historical layers and their potential effect on the buildings. Apart from auger holes and ground-researching investigations, there were GPR and electrical resistance tests of the matter below the cellars level as well as geochemical tests of the earth samples. The established level of undisturbed subsoil clearly shows that the endangered buildings are situated within the 30% slope of the original terrain, in which bottom level there are muds which easily change texture into fluid. In the stratigraphy, there was also established an organic layer of substantial thickness, which is completely unsuitable for construction. The mechanics of the building is affected by deposits of varied stability and also by the presence of rigid objects connected with historical
foundations. The existence of these factors manifested itself in the form of wall fractures in the area of convent, especially visible in kapelania, causing also disturbance of the floor level in the kapelania cellars. The observed loosening of the subsoil structure, possibly with a range greater than the area of the Bernardine Convent, is connected with a series of drainage works of deep excavations, in connection with a number of realized investments in the densely populated, historic part of Old Krakow. The development of the modern town within the net of historical layers demands constant monitoring of water and earth conditions of the subsoil. Both excessive drainage and water retention damage the stability of historical buildings and bring the threat of construction disaster.
the cellar rooms under the buildings near the Church. The aim of research is to determine the properties and stratigraphy of the earth in the subsoil of the endangered object, as well as of its immediate neighbourhood. Archaeological sources and their interdisciplinary interpretation in the context of the geological profiles conducted, based on the auger holes and narrow open pits, attest to a complex set of historical layers and their potential effect on the buildings. Apart from auger holes and ground-researching investigations, there were GPR and electrical resistance tests of the matter below the cellars level as well as geochemical tests of the earth samples. The established level of undisturbed subsoil clearly shows that the endangered buildings are situated within the 30% slope of the original terrain, in which bottom level there are muds which easily change texture into fluid. In the stratigraphy, there was also established an organic layer of substantial thickness, which is completely unsuitable for construction. The mechanics of the building is affected by deposits of varied stability and also by the presence of rigid objects connected with historical
foundations. The existence of these factors manifested itself in the form of wall fractures in the area of convent, especially visible in kapelania, causing also disturbance of the floor level in the kapelania cellars. The observed loosening of the subsoil structure, possibly with a range greater than the area of the Bernardine Convent, is connected with a series of drainage works of deep excavations, in connection with a number of realized investments in the densely populated, historic part of Old Krakow. The development of the modern town within the net of historical layers demands constant monitoring of water and earth conditions of the subsoil. Both excessive drainage and water retention damage the stability of historical buildings and bring the threat of construction disaster.
- by Aldona Garbacz-Klempka and +6
- •
- Geochemistry, Stratigraphy, Artifacts, Silts
In the Foothill of the Polish Flysch Carpathians numerous sandstone tors occur. The outer, exposed parts of the rocks are often covered by crust which is up to several centimeters thick. This crust, usually laminated, forms as a result of... more
In the Foothill of the Polish Flysch Carpathians numerous sandstone tors occur. The outer, exposed parts of the rocks are often covered by crust which is up to several centimeters thick. This crust, usually laminated, forms as a result of weathering processes. The laminae run parallel to the surface and differ from the internal part of the rocks in colour and composition. The hue and intensity of the colour can vary significantly. The objective of this study was to determine the types of iron compounds, which are probably responsible for the variable colouration and cementation of the weathering crust. Based on results of earlier works, 6 sampling locations were chosen including tors build of Istebna and Ciężkowice sandstones. A total of 31 samples were selected for laboratory analyses. Because of quite low total Fe contents in the studied samples, sequential chemical extractions and Mössbauer spectroscopy were applied besides standard mineralogical analyses (data not presented here...
- by Mariola Marszałek and +1
- •
In the Foothill of the Polish Flysch Carpathians numerous sandstone tors occur. The outer, exposed parts of the rocks are often covered by crust which is up to several centimeters thick. This crust, usually laminated, forms as a result of... more
In the Foothill of the Polish Flysch Carpathians numerous sandstone tors occur. The outer, exposed parts of the rocks are often covered by crust which is up to several centimeters thick. This crust, usually laminated, forms as a result of weathering processes. The laminae run parallel to the surface and differ from the internal part of the rocks in colour and composition. The hue and intensity of the colour can vary significantly. The objective of this study was to determine the types of iron compounds, which are probably responsible for the variable colouration and cementation of the weathering crust. Based on results of earlier works, 6 sampling locations were chosen including tors build of Istebna and Ciężkowice sandstones. A total of 31 samples were selected for laboratory analyses. Because of quite low total Fe contents in the studied samples, sequential chemical extractions and Mössbauer spectroscopy were applied besides standard mineralogical analyses (data not presented here...
- by Mariola Marszałek and +1
- •
The study was aimed at min er al og i cal and geo chem i cal char ac ter is tics of sec ond ary phases re lated to de te ri o ra tion of his - toric build ing ma te ri als. The in ves ti ga tions, car ried out in the Holy Trin ity Ba sil... more
The study was aimed at min er al og i cal and geo chem i cal char ac ter is tics of sec ond ary phases re lated to de te ri o ra tion of his -
toric build ing ma te ri als. The in ves ti ga tions, car ried out in the Holy Trin ity Ba sil ica in Kraków, Po land, fo cused on the south ern
facade of the 17th-cen tury Myszkowskis Cha pel, built of the Mio cene Piñczów lime stone. Lower part of the facade is cov ered
with a ce ment ren der, and the ex posed foun da tions are made of Ju ras sic lime stone and Cre ta ceous sand stone, both of lo cal
or i gin from the Kraków re gion and neigh bour ing Carpathians, in the form of ir reg u lar blocks bound with a ce ment mor tar. The
wall sur face ex hib its clear signs of dam age; from dark grey soil ing and scal ing to efflorescences. Sam pled ma te ri als, de te ri o -
rated, al tered crusts and efflorescences were an a lysed with op ti cal and scan ning elec tron mi cros copy, X-ray dif frac tion, and
Raman microspectroscopy meth ods. The sec ond ary min er als dis tin guished in clude abun dant gyp sum CaSO4·2H2O, less
com mon thenardite Na2SO4 (and/or mirabilite Na2SO4ÿ10H2O), aphthitalite (K, Na)3Na(SO4)2, darapskite
Na3(SO4)(NO3)·H2O, ettringite Ca6Al2(SO4)3(OH)12·26H2O, monosulphite Ca4Al2O6SO3·11H2O, as well as scarce ni tre
KNO3, nitratine NaNO3 and ha lite NaCl. Gyp sum usu ally forms sur face crusts and fills the pores in side some ma te ri als. The
efflorescences, sam pled from the ex posed foun da tions, con sisted of thenardite and/or mirabilite, aphthitalite and darapskite,
whereas ettringite and monosulphite were con nected with ce ment ren ders. Traces of ni tre, nitratine and ha lite were de tected
at var i ous el e ments of the cha pel facade and foun da tions. The or i gin of the salts is re lated to com po si tion and
physicochemical prop er ties of the build ing ma te ri als, as well as to anthropogenic fac tors.
Key words: stone de te ri o ra tion, sec ond ary salts, aphthitalite, darapskite.
toric build ing ma te ri als. The in ves ti ga tions, car ried out in the Holy Trin ity Ba sil ica in Kraków, Po land, fo cused on the south ern
facade of the 17th-cen tury Myszkowskis Cha pel, built of the Mio cene Piñczów lime stone. Lower part of the facade is cov ered
with a ce ment ren der, and the ex posed foun da tions are made of Ju ras sic lime stone and Cre ta ceous sand stone, both of lo cal
or i gin from the Kraków re gion and neigh bour ing Carpathians, in the form of ir reg u lar blocks bound with a ce ment mor tar. The
wall sur face ex hib its clear signs of dam age; from dark grey soil ing and scal ing to efflorescences. Sam pled ma te ri als, de te ri o -
rated, al tered crusts and efflorescences were an a lysed with op ti cal and scan ning elec tron mi cros copy, X-ray dif frac tion, and
Raman microspectroscopy meth ods. The sec ond ary min er als dis tin guished in clude abun dant gyp sum CaSO4·2H2O, less
com mon thenardite Na2SO4 (and/or mirabilite Na2SO4ÿ10H2O), aphthitalite (K, Na)3Na(SO4)2, darapskite
Na3(SO4)(NO3)·H2O, ettringite Ca6Al2(SO4)3(OH)12·26H2O, monosulphite Ca4Al2O6SO3·11H2O, as well as scarce ni tre
KNO3, nitratine NaNO3 and ha lite NaCl. Gyp sum usu ally forms sur face crusts and fills the pores in side some ma te ri als. The
efflorescences, sam pled from the ex posed foun da tions, con sisted of thenardite and/or mirabilite, aphthitalite and darapskite,
whereas ettringite and monosulphite were con nected with ce ment ren ders. Traces of ni tre, nitratine and ha lite were de tected
at var i ous el e ments of the cha pel facade and foun da tions. The or i gin of the salts is re lated to com po si tion and
physicochemical prop er ties of the build ing ma te ri als, as well as to anthropogenic fac tors.
Key words: stone de te ri o ra tion, sec ond ary salts, aphthitalite, darapskite.
- by Mariola Marszałek and +1
- •
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... more
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.
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... more
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.