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International Journal of Architectural Heritage

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Application of Optical Microscopy and Scanning Electron Microscopy to the Study of Stone Weathering: A Cracow Case Study
Mariola Marszaek
a a

AGHUniversity of Science and Technology, Department of Mineralogy, Petrography and Geochemistry, Cracow, Poland Available online: 08 Feb 2008

To cite this article: Mariola Marszaek (2008): Application of Optical Microscopy and Scanning Electron Microscopy to the Study of Stone Weathering: A Cracow Case Study, International Journal of Architectural Heritage, 2:1, 83-92 To link to this article: http://dx.doi.org/10.1080/15583050701646695

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International Journal of Architectural Heritage, 2: 8392, 2008 Copyright Taylor & Francis Group, LLC ISSN: 1558-3058 print / 1558-3066 online DOI: 10.1080/15583050701646695

APPLICATION OF OPTICAL MICROSCOPY AND SCANNING ELECTRON MICROSCOPY TO THE STUDY OF STONE WEATHERING: A CRACOW CASE STUDY Mariola Marszaek
AGHUniversity of Science and Technology, Department of Mineralogy, Petrography and Geochemistry, Cracow, Poland

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Optical microscopy in transmitted and reflected light and scanning electron microscopy with a field emission gun combined with microprobe analysis energy-dispersive spectroscopy (EDS) were used for characterizing the energy-dispersive spectroscopy changes in the weathered stone layers and, particularly, in studying microscopic particles. Additionally, the electron backscattered diffraction (EBSD) technique provided crystallographic information for the particles examined. Five main categories of anthropogenic particles were distinguished: gypsum crystals, solid glass particles, dendritic iron oxides, crystalline iron oxides, and partly coked carbon particles. From the crystallographic information obtained with the EBSD technique, most of iron oxides particle was identified as hematite. KEY WORDS: stone weathering, black crust, anthropogenic particles, optical microscopy, scanning electron microscopy

1. INTRODUCTION The phenomena of the stone weathering include the physical and chemical processes. They are complex and result in difficulties in identifying individual causes of weathering of the stone. The physical processes involve the disintegration of the rock with no chemical alteration, although their relationship to chemical weathering is very close. The most pronounced physical weathering processes are: 1) natural: frostthaw action, insolation, and plant-root damage, and 2) anthropogenic: patina removal and vandalism. Chemical processes can be divided into: dissolution of material grains, and cements; complexing, chelating, and crystallization of new phases; hydratation; hydrolysis; and oxidation/bacterial reduction. The last four processes result in physical stress (force) for example, hydraulic pressure is connected, with crystal growth and hydratation of salts that can exist in more than one hydration stage. Thus these processes can be mentioned among physical processes as well and described as physicochemical reactions. Factors leading to the damage of stone elements are both external (climatic and microclimatic, anthropogenic, and biogenic) and internal, stone-inherited (the type of rock, its structure, and mineral composition). The degree of damage of elements made of the same type of stone depends on the differences in the mineral composition,
Received 10 October 2006; accepted 23 August 2007. Address correspondence to Mariola Marszalek, AGHUniversity of Science and Technology, Department of Mineralogy, Petrography and Geochemistry, al. Mickiewicza 30, 30-059 Cracow, Poland. E-mail: mmarszal@agh.edu.pl 83

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texture, structure, and certain surface properties of the stone varieties used. The widespread development of black patinas on buildings is a decay feature that predominates in urban atmosphere. The changes during weathering include mainly deposition of anthropogenic particles, formation of new minerals, especially salts, and iron migration within building stones. All these processes can additionally affect aesthetics of building stone surfaces. Studies on the composition of the black crusts have revealed particularly the presence of fly-ashes (porous carbon particles, smooth and porous glass spheres, iron oxides) and gypsum. Air pollution is often viewed as dominant factor in causing stone damage, particularly in the case of outdoor exposition. Sulfur dioxide (SO2) has long been recognized as the primary gaseous component of human-polluted air. SO2 with nitrogen oxides (NOx) are the most harmful for stone materials and are the major source of soluble salts, mainly sulfates and nitrates. Additionally the salts may be carried into building from the basement, rising by capillarity from the soil itself, or from the soil containing deicing or other chemicals, or as aerosols brought by winds. In urban atmosphere, oxidation of SO2 to sulfate is catalyzed by metals emitted from power plants. The natural emissions of SO2 to the atmosphere originate mainly from biological processes and volcanic activity; however, in the industrial areas, the anthropogenic emissions concentrate and are dominant. Biological processes and lightning are the natural sources of the NOx, but today the main sources are anthropogenic, i.e., fossil fuel combustion and automobile traffic. The fly-ash grains are emitted into the atmosphere mainly due to the combustion of fuels in power plants, local boiler houses and vehicles; they originate also in steelwork and other plants. They are the carriers of numerous trace elements as well, including heavy metals (Cd, Pb, Cr, Ni, Zn, Cu, and Fe) and aromatic and aliphatic hydrocarbons (Camuffo et al., 1983; Manecki et al., 1997; Assuet et al., 1999; Bugini et al., 2000; Marszalek 1994 and 2004). Carbonaceous fly-ash particles have a very strong physicochemical reactivity (Del Monte et al., 1981 and 1984, Del Monte and Sabbioni, 1984, Assuet et al., 1996 and 1999) that leads to adherence of these particles to all surfaces (not only carbonate stones), where they initiate formation of gypsum crystals and development of embryonic black crusts (Assuet et al., 1999). The presence of some metals, such as Fe, V, and Ni can favor the crystallization of other authigenic substances, mainly gypsum (Del Monte and Sabbioni, 1987; Assuet et al., 1999). In recent decades the SO2 emissions, and thus SO2 deposition and accumulation on cultural heritage objects, have decreased. The deterioration of the stone monuments is attributed to a large extent to the combustion of fossil fuels, mainly motor vehicles. This results in increasing levels of NOx, ozone, and particulates in the atmosphere (Brimblecombe, 2004; Saiz-Jimenez et al., 2004). In the field of cultural heritage, surface and microanalytical techniques yield valuable information on the progress of weathering onsite and in laboratory simulations. The optical microscope and scanning electron microscope (SEM) have been widely used as analytical tools for description of the surface in the weathering study for many years (among others, Del Monte et al., 1981 and 1984; Manecki et al., 1997; Van Grieken and Fobe, 1990; Marszalek 1994, 2004 and 2005; Michalik and Wilczynska-Michalik, 1997). The application of field emission scanning microscopy and the chemical characteristics determined by energy-dispersive X-ray analysis (EDAX) equipment allow characterization of changes in the composition of the weathered stone surfaces better than conventional scanning microscopy.
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Additionally, application of the electron backscattered diffraction (EBSD) technique provides crystallographic information on the particles examined. The EBSD technique is based on the weak diffraction pattern that forms when a focused, stationary, primary electron beam strikes a polished sample, backscatters, and diffracts. The diffraction pattern is formed on a fluorescent screen and transferred by a camera to the computer. Rapid developments in both hardware and software in the past few years have made EBSD easy to use and ideal for the rapid analysis of microstructures of crystalline materials. The diffraction pattern is therefore characteristic of the crystal structure and space orientation of the crystal. EBSD is very helpful when using the SEM-EDS technique, we observe and analyze minerals that exist in different crystal structures and have the same chemical formula (polymorphs) or have the same (qualitative) elemental composition, which not always directly identifies the phase present (e.g., Fe2O3/Fe3O4; MgSO46H2O/ MgSO47H2O). Thus the detailed analyses of the type and composition of particulate matter seems to be important for explaining their role in the phenomena of stone decay in various European cities that can differ in terms of air pollution. 2. MATERIALS AND METHODS The material analyzed included outer layers of weathered stones collected from the architectonic details exposed to anthropogenic influences in the historical buildings of Cracow, Poland. Among the natural building stones used in Cracow monuments the most popular are limestones and sandstones:  limestones from:  * Pinczow a Tertiary light cream rock;  * CracowCzestochowa upland a Jurassic white compact rock; and  * Debnik a Devonian black, compact limestone; and  sandstones from the Carpathian Mountains, of the Lower Cretaceous to Middle Tertiary age, particularly the Istebna sandstones cream yellowish or even reddish, medium- to coarse-grained. Mineralogies, structures, and textures of the stones control, as major factors, the rate of a stone decay. The most prone to alterations are Pinczow limestones and sandstones from the Carpathians (Manecki et al., 1997; Marszalek, 1994 and 2004). The samples were collected from famous historical objects in Cracow, among others, the Cloth Hall and St. Andrews church (Pinczow limestones, Istebna sand stones); Holy Trinitys church (Pinczow limestones); St. Adalberts church and head stones from the Rakowice cemetery (Debnik limestones); and the Florianska Gate, City Hall Tower, and Ojcow castle near Cracow (Jurassic limestones). Three types of changes can be distinguished at the surface of the stones analyzed:  areas exposed to the washing action of rain, which mainly contain original compo nents of the stone partly grey or in the original color of the stone;  areas along the borders of stone elements exposed to and sheltered from running water grey or black, covered mainly by dendritic crusts; and  areas in sheltered parts of architectonic elements covered by black crusts. The black and grey crusts, which contain a lot of anthropogenic particles, were chosen for analyses. Two types of samples were prepared: 1) universal polished thin sections
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cut perpendicularly to the stone surface; and 2) grain fractions, insoluble in 6M HCl, of the outer layers of weathered architectonic details. The samples were observed applying optical microscopy in transmitted and reflected light and SEM combined with microprobe analysis EDS. Secondary electron images and back-scattered electron images were studied. The EBSD patterns were used to characterize crystal structure of some anthropogenic particles. The research equipment included an optical microscope Olympus BX51 (Olympus Optical Co., GMBH, Hamburg, Germany) and a field emission scanning electron microscope FEI Quanta 200 FEG (FEI Company, Oregon, USA) with an energy-dispersive spectrometer EDAX and an EBSD attachment.

3. RESULTS

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The qualitative composition of the crust, in each type of the stones analyzed, is similar. Only quantitative differences were observed. Four main categories of anthropogenic particles have been distinguished: gypsum crystals, solid glass particles, two types of iron oxides, and partly coked carbon particles. The same particles (excluding gypsum) or their aggregates were observed in the acid-insoluble grain fraction. 3.1. Gypsum Crystals Surfaces of some elements from historical objects are covered by gypsum layers with thickness up to approximately 200 mm ( Figure 1). The gypsum is developed as fine, microcrystalline to cryptocrystalline crystals, and euhedral, sometimes subhedral and even anhedral (Figure 2). Due to a small size of the crystals, they are almost isotropic in transmitted light. The SEM-EDS maps of sulfur distributions show enrichment in this element resulting from the presence of gypsum (Figure 3). Gypsum concentrates in subsurface layers of the stone, but was detected also inside the stone in pores and cracks (Figure 4). Formation of hydrated calcium sulfate is an effect of the exposure of stones to the SO2-containing atmosphere (reaction of acid rain with calcite). Local staining with iron hydroxides was occasionally observed (Figure 5), but their detection by SEMEDS is difficult because of a very low iron concentration.

Figure 1. Polished cross section of a dendritic crust with an average thickness of 200 mm, with two alteration layers: an external of microcrystalline gypsum and deposits of dust (glass particles, iron oxides particles, and partly coked carbon particles) and an internal one of micro- to cryptocrystalline gypsum. A) Jurassic limestone; B) Devonian Debnik limestone. (optical microscope, transmitted light, 1N). INTERNATIONAL JOURNAL OF ARCHITECTURAL HERITAGE 2(1): 8392

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Figure 2. Scanning electron microscope micrograph of A) euhedral and B) anhedral gypsum crystals.

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Figure 3. Concentration of S, Si, and Fe within cross section of the crust on the Devonian limestone (scanning electron microscopeenergy-dispersive spectroscopy attachment).

3.2. Solid Glass Particles Mostly spherical glass particles were recognized in transmitted and reflected light as colorless or grey particles of very small sizes up to 20 mm. SEM observations show their characteristic smooth appearance, but some reveal dendritic crystallization of iron oxides. The glass spheres are composed of silicon and aluminum
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Figure 4. Concentration of S within cross section of the crust on the Jurassic limestone (scanning electron microscopeenergy-dispersive spectroscopy attachment).

Figure 5. Fe-rich zones at the surface of Jurassic limestone (optical microscope, transmitted light, 1N).

with minor amounts of iron and other metals, such as titanium. The presence of Si on the surface of the limestones analyzed is very often connected just with such of solid glass particles (Figure 3). There are also small amounts of Ca and K (Figure 6). The composition of these smooth particles is similar to that of clay impurities in coal. 3.3. Iron Oxides Two types of iron oxides were observed:  dendritic iron oxides particles (mostly spherical), containing variable amounts of glassy matrix; and  crystalline iron oxide particles (mostly spherical), containing trace amounts of glassy matrix (SEM-EDS).
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Figure 6. Solid glass particles (scanning electron microscopeenergy-dispersive spectroscopy attachment) and graph of their chemical composition.

Most of dendritic iron particles are similar in size to the solid glass particles; however the former can be distinguished from the latter by being much brighter both in reflected light (Figure 7) and in SEMback-scattered electron mode due to the presence of abundant dendritic iron oxide crystallites in a generally subordinate glassy matrix (Figure 8A). The maps of Fe distribution confirm the presence such particles on the stone surface (Figure 3). Additionally, two types of oxides can be distinguished in reflected light: a darker one resembling magnetite Fe3O4 and a brighter one resembling hematite Fe2O3. These two oxides are often intimately intergrown and indicate that the dendrites initially formed in the reducing part of the furnace as Fe3O4 and later oxidized to Fe2O3 (Del Monte et al., 1976; Ramsden and Shibaoka, 1982). Crystalline iron oxide particles are similar in size to dendritic particles but they contain only traces of glassy matrix (Figure 8B). Crystallographic information obtained with the EBSD technique allows characterization of most iron oxide particles as hematite (Figure 9).

Figure 7. The outer layer of Jurassic limestone with glass spherical particles (gray) and iron oxides (bright) (optical microscope, reflected light, 1N). INTERNATIONAL JOURNAL OF ARCHITECTURAL HERITAGE 2(1): 8392

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Figure 8. A) Dendritic iron oxide and B) crystalline iron oxide particles (scanning electron microscope energy-dispersive spectroscopy attachment) and graphs of their chemical composition.

Figure 9. A) Iron oxide particle analyzed by B) electron backscattered diffraction as shown in C).

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Figure 10. Scanning electron microscope image of porous carbonaceous fly ash particle in a black crust.

3.4. Partly Coked Carbon Particles Partly coked carbon particles are porous and mostly irregular. They are rich mainly in C and S, contain variable amounts of glass matrix and originate from combustion of solid and liquid fuels (Figure 10). 4. CONCLUSIONS  Application of complex microscope methods: optical microscopy in transmitted and reflected light, SEM with a field emission gun combined with microprobe analysis EDS and back-scattered electron mode allows characterization of the changes in the weathered stone layers and particularly studying microscope-sized particles.  The maps of distribution of some elements, mainly S, are useful in determining the range of stone weathering and its penetration by newly formed anthropogenic phases.  The EBSD technique provides crystallographic information on samples analyzed and helps solving some problems with identification of very small particles (e.g., hematitemagnetite).  Determining with higher precision the changes that occur within stone surface layers during weathering can result in better understanding of weathering mechanisms and decisions about the choice of intervention strategies applied. ACKNOWLEDGMENTS The author thanks A. Gawel, M.Sc., of AGHUniversity of Science and Technology for electron backscattered diffraction analyses. The help of Dr. A. Skowronski of AGHUniversity of Science and Technology is very much appreciated. This study was supported by the AGHUniversity of Science and Technology project No. 11.11.140.158.
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