Black Crust from Historic Buildings as a Natural Indicator of Air Pollution: A Case Study of the Lipowiec Castle, Babice, Southern Poland
Abstract
:1. Introduction
2. Site and Monument
3. Materials and Methods
4. Results
4.1. Raman Micro-Spectroscopy
4.2. SEM-EDS
5. Discussion
6. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- Doehne, E.; Price, C.A. Stone Conservations: An Overview of Current Research, 2nd ed.; Getty Conservation Institute: Los Angeles, CA, USA, 2010; 159p. [Google Scholar]
- Lefèvre, R.A.; Ausset, P. Atmospheric pollution and building materials: Stone and glass. In Natural Stone, Weathering Phenomena, Conservation Strategies and Case Studies; Siegesmund, S., Weiss, T., Vollbrecht, A., Eds.; Geological Society: London, UK; Special Publications: London, UK, 2002; Volume 205, pp. 329–345. [Google Scholar] [CrossRef]
- Saiz-Jimenez, C.; Hermosin, B. Black crusts in the European built environment. Corros. Rev. 2004, 22, 381–393. [Google Scholar] [CrossRef]
- Toniolo, L.; Zerbi, C.M.; Bugini, R. Black layers on historical architecture. Environ. Sci. Pollut. Res. 2009, 16, 218–226. [Google Scholar] [CrossRef] [PubMed]
- Bonazza, A.; Sabbioni, C.; Ghedini, N. Quantitative data on carbon fractions in interpretation of black crusts and soiling on European built heritage. Atmos. Environ. 2005, 39, 2607–2618. [Google Scholar] [CrossRef]
- Grossi, C.M.; Brimblecombe, P. Effect of Long-Term Changes in Air Pollution and Climate on the Decay and Blackening of European Stone Buildings. In Building Stone Decay: From Diagnosis to Conservation; Prikryl, R., Smith, B.J., Eds.; Geological Society: London, UK; Special Publications: London, UK, 2007; Volume 271, pp. 117–130. [Google Scholar] [CrossRef]
- Fronteau, G.; Schneider-Thomachot, C.; Chopin, E.; Barbin, V.; Mouze, D.; Pascal, A. Black-Crust Growth and Interaction with Underlying Limestone Microfacies. In Natural Stone Resources for Historical Monuments; Prikryl, R., Smith, B.J., Eds.; Geological Society: London, UK; Special Publications: London, UK, 2010; Volume 333, pp. 25–34. [Google Scholar] [CrossRef]
- Perez-Monserrat, E.M.; Varas-Muriel, M.J.; De Buergo, M.A.; Fort, R. Black Layers of Decay and Color Patterns on Heritage Limestone as Markers of Environmental Change. Geosciences 2016, 6, 4. [Google Scholar] [CrossRef]
- Cano, H.; Ríos-Rojas, J.F.; Hernández-Fernández, J.; Bernal Herrera, W.; Bautista Betancur, M.; De La Hoz Vélez, L.; Agámez González, L. Impact of Environmental Pollution in the Sustainability of Architectural Heritage: Case Study from Cartagena of India, Colombia. Sustainability 2022, 14, 189. [Google Scholar] [CrossRef]
- Brimblecombe, P.; Grossi, C.M. Aesthetic thresholds and blackening of stone buildings. Sci. Total Environ. 2005, 349, 175–189. [Google Scholar] [CrossRef] [PubMed]
- Schiavon, N.; Chiavari, G.; Fabbri, D. Soiling of limestone in an urban environment characterized by heavy vehicular exhaust emissions. Environ. Geol. 2004, 46, 448–455. [Google Scholar] [CrossRef]
- Charola, A.; Pühringer, J.; Steiger, M. Gypsum: A review of its role in the deterioration of building materials. Environ. Geol. 2007, 52, 339–352. [Google Scholar] [CrossRef]
- Barca, D.; Belfiore, C.M.; Crisci, G.M.; La Russa, M.F.; Pezzino, A.; Ruffolo, S.A. Application of laser ablation ICP-MS and traditional techniques to the study of black crusts on building stones: A new methodological approach. Environ. Sci. Poll. Res. 2010, 17, 1433–1447. [Google Scholar] [CrossRef]
- Barca, D.; Comite, V.; Belfiore, C.M.; Bonazza, A.; La Russa, M.F.; Ruffolo, S.A.; Crisci, G.M.; Pezzino, A.; Sabbioni, C. Impact of air pollution in deterioration of carbonate building materials in Italian urban environments. Appl. Geochem. 2014, 48, 122–131. [Google Scholar] [CrossRef]
- Ruffolo, S.A.; Comite, V.; La Russa, M.F.; Belfiore, C.M.; Barca, D.; Bonazza, A.; Crisci, G.M.; Pezzino, A.; Sabbioni, C. An analysis of the black crusts from the Seville Cathedral: A challenge to deepen the understanding of the relationships among microstructure, microchemical features and pollution sources. Sci. Tot. Environ. 2015, 502, 157–166. [Google Scholar] [CrossRef] [PubMed]
- Morillas, H.; Maguregui, M.; García-Florentino, C.; Carrero, J.A.; Madariaga, J.M. The cauliflower-like black crusts on sandstones: A natural passive sampler to evaluate the surrounding environmental pollution. Environ. Res. 2016, 17, 218–232. [Google Scholar] [CrossRef] [PubMed]
- Calparsoro, E.; Maguregui, M.; Giakoumaki, A.; Morillas, H.; Madariaga, J.M. Evaluation of black crust formation and soiling process on historical buildings from the Bilbao metropolitan area (north of Spain) using SEM-EDS and Raman microscopy. Environ. Sci. Pollut. Res. 2017, 24, 9468–9480. [Google Scholar] [CrossRef] [PubMed]
- Amoroso, G.G.; Fassina, V. Stone Decay and Conservation. Atmospheric Pollution, Cleaning, Consolidation and Protection; Elsevier: Amsterdam, The Netherlands, 1983; 449p. [Google Scholar]
- Johansson, L.G.; Lindqvist, O.; Mangio, R.E. Corrosion of calcareous stones in humid air containing SO2 and NO2. Dur. Build. Mat. 1988, 5, 439–449. [Google Scholar]
- Moropoulou, A.; Bisbikou, K.; Van Grieken, R.; Zezza, F.; Macri, F. Origin and growth of weathering crusts on ancient marbles in industrial atmosphere. Atmos. Environ. 1998, 32, 967–982. [Google Scholar] [CrossRef]
- Charola, A.E.; Ware, R. Acid deposition and the deterioration of stone: A brief review of a broad topic. In Natural Stone, Weathering Phenomena, Conservation Strategies and Case Studies; Siegesmund, S., Weiss, T., Vollbrecht, A., Eds.; Geological Society: London, UK; Special Publications: London, UK, 2002; Volume 205, pp. 393–406. [Google Scholar] [CrossRef]
- ICOMOS. 2008. Available online: http://www.icomos.org/en/component/content/article/116-englishcategories/resources/publications/261-monumentsasites-xv (accessed on 10 April 2024).
- La Russa, M.F.; Comite, V.; Aly, N.; Barca, D.; Fermo, P.; Rovella, N.; Antonelli, F.; Tesser, E.; Aquino, M.; Ruffolo, S.A. Black crusts on Venetian built heritage, investigation on the impact of pollution sources on their composition. Eur. Phys. J. Plus 2018, 133, 370. [Google Scholar] [CrossRef]
- Machill, S.; Althaus, K.; Krumbein, W.E.; Stegew, W.E. Identification of organic compounds extracted from black weathered surfaces of Saxonean sandstones, correlation with atmospheric input and rock inhabiting microflora. Org. Geochem. 1997, 27, 79–97. [Google Scholar] [CrossRef]
- Sýkorová, I.; Havelcová, M.; Zeman, A.; Trejtnarová, H. Carbon air pollution reflected in deposits on chosen building materials of Prague Castle. Sci. Total Environ. 2011, 409, 4606–4611. [Google Scholar] [CrossRef] [PubMed]
- Papida, S.; Marphy, W.; May, E. Enhancement of physical weathering of building stones by microbial populations. Int. Biodeter. Biodegr. 2000, 46, 305–317. [Google Scholar] [CrossRef]
- De Belie, N. Microorganisms versus stony materials: A love–hate relationship. Mat. Struct. 2010, 43, 1191–1202. [Google Scholar] [CrossRef]
- Marszałek, M.; Dudek, K.; Czerny, J.; Gaweł, A. Mineralogical and geochemical studies of secondary mineral assemblages related to deterioration of building materials. Geol. Quart. 2019, 63, 683–698. [Google Scholar] [CrossRef]
- Marszałek, M.; Dudek, K.; Gaweł, A. Cement Render and Mortar and Their Damages Due to Salt Crystallization in the Holy Trinity Church, Dominicans Monastery in Cracow, Poland. Minerals 2020, 10, 641. [Google Scholar] [CrossRef]
- Gaylarde, C.C.; Baptista-Neto, J.A. Microbiologically induced aesthetic and structural changes to dimension stone. npj Mater. Degrad. 2021, 5, 33. [Google Scholar] [CrossRef]
- Pozo-Antonio, J.S.; Cardell, C.; Comite, V.; Fermo, P. Characterization of black crusts developed on historic stones with diverse mineralogy under different air quality environments. Environ. Sci. Pollut. Res. 2022, 29, 29438–29454. [Google Scholar] [CrossRef] [PubMed]
- Islam, N.; Roy, K.; Barman, P.; Rabha, S.; Bora, H.K.; Khare, P.; Konwar, R.; Saikia, B.K. Chemical and toxicological studies on black crust formed over historical monuments as a probable health hazard. J. Hazard. Mat. 2024, 464, 132939. [Google Scholar] [CrossRef] [PubMed]
- Török, Á.; Licha, T.; Simon, K.; Siegesmund, S. Urban and rural limestone weathering; the contribution of dust to black crust formation. Environ. Earth. Sci. 2011, 63, 675–693. [Google Scholar] [CrossRef]
- Randazzo, L.; Collina, M.; Ricca, M.; Barbieri, L.; Bruno, F.; Arcudi, A.; La Russa, M.F. Damage Indices and Photogrammetry for Decay Assessment of Stone-Built Cultural Heritage: The Case Study of the San Domenico Church Main Entrance Portal (South Calabria, Italy). Sustainability 2020, 12, 5198. [Google Scholar] [CrossRef]
- Camuffo, D.; Del Monte, M.; Sabbioni, C. Origin and growth mechanisms of the sulfated crusts on urban limestone. Water Air Soil Poll. 1983, 19, 351–359. [Google Scholar] [CrossRef]
- Małkowska-Holcerowa, T. Lipowiec dawny zamek biskupów krakowskich. (Lipowiec the Former Castle of Cracow’s Bishops); Wyd. PTTK “KRAJ”: Warszawa, Poland, 1989; 44p, (In Polish with English Summary). [Google Scholar]
- Siedlecki, S. Utwory geologiczne obszaru pomiędzy Chrzanowem a Kwaczałą. (Geology of the area between Chrzanów and Kwaczała). Biul. Inst. Geol. 1952, 60, 1–230, (In Polish with English Summary). [Google Scholar]
- Płonczyński, J.; Preidl, M.; Kurek, S. Objaśnienia do szczegółowej mapy geologicznej Polski 1:50 000 Arkusz Chrzanów (971). (Explanations to Detailed Geological Map of Poland 1:50000 Sheet Chrzanów (971)); Państwowy Instytut Geologiczny—Państwowy Instytut Badawczy: Warszawa, Poland, 2015; 41p. (In Polish) [Google Scholar]
- Myszkowska, J. Litofacje i sedymentacja dolomitów diploporowych (środkowy wapień muszlowy) wschodniej części obszaru śląsko-krakowskiego. (Lithofacies and Sedimentation of Diplopora Dolomite (Middle Muschelkalk) in the East Part of the Cracovian-Silesian Region). Ann. Soc. Geol. Pol. 1992, 62, 19–62, (In Polish with English Summary). [Google Scholar]
- Wyszomirski, P.; Przytuła, S. Charakterystyka surowcowa kruszywa dolomitowego na przykładzie kopaliny z Libiąża (region śląsko-krakowski). (Raw mineral characteristics of dolostone aggregates: An example of the rock from Libiąż (Cracow-Silesian region)). Zesz. Nauk. IGSMiE PAN 2010, 79, 213–222, (In Polish with English Abstract). [Google Scholar]
- Downs, R.T.; Hall-Wallace, M. A Database of Crystal Structures. Published in the American Mineralogist and The Canadian Mineralogist and Its Use as a Resource in the Classroom. In Proceedings of the 18th General Meeting of the International Mineralogical Association, Edinburgh, UK, 1–6 September 2002; p. 128. [Google Scholar]
- Wang, A.; Freeman, J.J.; Jolliff, B.L.; Chou, I. Sulfates on Mars: A systematic Raman spectroscopic study of hydration states of magnesium sulfates. Geochim. Cosmochim. Acta 2006, 70, 6118–6135. [Google Scholar] [CrossRef]
- Culka, A.; Košek, F.; Drahota, P.; Jehlička, J. Use of miniaturized Raman spectrometer for detection of sulfates of different hydration states—Significance for Mars studies. Icarus 2014, 243, 440–453. [Google Scholar] [CrossRef]
- Jehlička, J.; Culka, A.; Košek, F. Obtaining Raman spectra of minerals and carbonaceous matter using a portable sequentially shifted excitation Raman spectrometer—A few examples. J. Raman Spectr. 2017, 48, 1583–1589. [Google Scholar] [CrossRef]
- Steiger, M.; Linnow, K.; Juling, H.; Gülker, G.; Jarad, A.; Brüggerhoff, S.; Kirchner, D. Hydration of MgSO4·H2O and Generation of Stress in Porous Materials. Cryst. Growth Des. 2008, 8, 336–343. [Google Scholar] [CrossRef]
- Mernag, T.P.; Cooney, R.P.; Johnson, R.A. Raman Spectra of Graphon Carbon Black. Carbon 1984, 22, 39–42. [Google Scholar] [CrossRef]
- Lee, K.O.; Cole, R.; Sekar, R.; Choi, M.Y.; Kang, J.S.; Bae, C.S.; Shin, H.D. Morphological Investigation of the Microstructure, Dimensions, and Fractal Geometry of Diesel Particulates. Proc. Combust. Inst. 2002, 29, 647–653. [Google Scholar] [CrossRef]
- Soewono, A.; Rogak, S. Morphology and Raman Spectra of Engine-Emitted Particulates. Aerosol Sci. Technol. 2011, 45, 1206–1216. [Google Scholar] [CrossRef]
- Sadezky, A.; Muckenhuber, H.; Grothe, H.; Niessner, R.; Pöschl, U. Raman Spectra of Soot and Related Carbonaceous Materials: Spectral Analysis and Structural Information. Carbon 2005, 43, 1731–1742. [Google Scholar] [CrossRef]
- Schito, A.; Romano, C.; Corrado, S.; Grido, D.; Poe, B. Diagenetic thermal evolution of organic matter by Raman spectroscopy. Org. Geochem. 2017, 106, 57–67. [Google Scholar] [CrossRef]
- Henry, D.G.; Jarvis, I.; Gillmore, G.; Stephenson, M. Raman spectroscopy as a tool to determine the thermal maturity of organic matter: Application to sedimentary, metamorphic and structural geology. Earth-Sci. Rev. 2019, 198, 102936. [Google Scholar] [CrossRef]
- Chhowalla, M.; Ferrari, A.C.; Robertson, J.; Amaratunga, G.A. Evolution of sp2 Bonding with Deposition Temperature in Tetrahedral Amorphous Carbon Studied by Raman Spectroscopy. Appl. Phys. Lett. 2000, 76, 1419–1421. [Google Scholar] [CrossRef]
- Ferrari, A.C.; Robertson, J. Interpretation of Raman Spectra of Disordered and Amorphous Carbon. Phys. Rev. B 2000, 61, 14095–14107. [Google Scholar] [CrossRef]
- Tuinstra, F.; Koenig, J.L. Raman Spectrum of Graphite. Chem. Phys. 1970, 53, 1126–1130. [Google Scholar] [CrossRef]
- Marszałek, M. Identification of secondary salts and their sources in deteriorated stone monuments using micro-Raman spectroscopy, SEM-EDS and XRD. J. Raman Spectr. 2016, 47, 1473–1485. [Google Scholar] [CrossRef]
- Adar, F. Carotenoids—Their Resonance Raman Spectra and How They Can Be Helpful in Characterizing a Number of Biological Systems. Spectroscopy 2017, 32, 12–20. Available online: https://www.spectroscopyonline.com/authors/fran-adar (accessed on 23 February 2024).
- Kloppmann, W.; Bromblet, P.; Vallet, J.M.; Vergès-Belmin, V.; Rolland, O.; Guerrot, C.; Gosselin, C. Building materials as intrinsic sources of sulphate: A hidden face of salt weathering of historical monuments investigated through multi-isotope tracing (B, O, S). Sci. Total Env. 2011, 409, 1658–1669. [Google Scholar] [CrossRef]
- Ishihara, J.; Takahashi, H. Raman spectral analysis of microbial pigment compositions in vegetative cells and heterocysts of multicellular cyanobacterium. Biochem. Biophys. Rep. 2023, 34, 101469. [Google Scholar] [CrossRef] [PubMed]
- Pietras, B.G. The Origin of Dust Particles in Atmospheric Air in Krakow (Poland) (Atmospheric Background). Land 2022, 11, 155. [Google Scholar] [CrossRef]
- Zioła, N.; Banasik, K.; Jabłońska, M.; Janeczek, J.; Błaszczak, B.; Klejnowski, K.; Mathews, B. Seasonality of the airborne ambient soot predominant emission sources determined by Raman microspectroscopy and thermo-optical method. Atmosphere 2021, 12, 768. [Google Scholar] [CrossRef]
- Smołka-Danielowska, D. Trace elements and mineral composition of waste produced in the process of combustion of solid fuels in individual household furnaces in the Upper Silesian Industrial Region (Poland). Environ. Socio-Econ. Stud. 2015, 3, 30–38. [Google Scholar] [CrossRef]
- Smolka-Danielowska, D.; Fiedor, D. Potentially toxic elements in fly ash dependently of applied technology of hard coal combustion. Environ. Sci. Pollut. Res. 2018, 25, 25091–25097. [Google Scholar] [CrossRef] [PubMed]
- Sass-Gustkiewicz, M. Revised and completed paragenetic order of minerals in the Pomorzany lead-zinc deposit. Upper Silesian Region, Poland. Mineral. Pol. 1997, 28, 46–80. [Google Scholar]
- Mikulski, S.Z.; Oszczepalski, S.; Sadłowska, K.; Chmielewski, A.; Małek, R. Występowanie pierwiastków towarzyszących i krytycznych w wybranych udokumentowanych złożach rud Zn-Pb, Cu-Ag, Fe-Ti-V, Mo-Cu-W, Sn, Au-Asi Ni w Polsce. (The occurrence of associated and critical elements in the selected documented Zn-Pb, Cu-Ag, Fe-Ti-V, Mo-Cu-W, Sn, Au-As and Ni deposits in Poland). Biul. Państwowego Inst. Geol. 2018, 472, 21–52, (In Polish with English Abstract). [Google Scholar] [CrossRef]
- Cabała, J. Metale ciężkie w środowisku glebowym olkuskiego rejonu eksploatacji rud Zn-Pb. (Heavy Metals in Ground Soil Environment of the Olkusz Area of Zn-Pb Ore Exploitation); Silesia Univeristy Press: Katowice, Poland, 2009; 130p, (In Polish with English Summary); Available online: http://hdl.handle.net/20.500.12128/3415 (accessed on 23 February 2024).
- Anameric, B.; Komar Kawatra, S. Direct iron smelting reduction processes Mineral Processing and Extractive Metallurgy Review. Int. J. 2008, 30, 1–51. [Google Scholar] [CrossRef]
- Jabłońska, M.; Rachwał, M.; Wawer, M.; Kądziołka-Gaweł, M.; Teper, E.; Krzykawski, T.; Smołka-Danielowska, D. Mineralogical and chemical specificity of dusts originating from iron and non-ferrous metallurgy in the light of their magnetic susceptibility. Minerals 2021, 11, 216. [Google Scholar] [CrossRef]
- Marszałek, M. Application of optical microscopy and scanning electron microscopy to the study of stone weathering: A Cracow case study. Int. J. Archit. Herit. 2008, 2, 83–92. [Google Scholar] [CrossRef]
- Del Monte, M.; Nanni, T.; Tagliazucca, M. The origin of black magnetic spherules through a study of their chemical, physical and mineralogical characteristics. Annali di Geofis. 1976, 29, 9–25. [Google Scholar] [CrossRef]
- Ramsden, A.R.; Shibaoka, M. Characterization and analysis of individual fly-ash particles from coal-fired power stations by a combination microscopy and quantitative electron microprobe analysis. Atmos. Environ. 1982, 16, 2191–2206. [Google Scholar] [CrossRef]
- Rożek, D.; Nadłonek, W.; Cabała, J. Forms of heavy metals (Zn, Pb, Cd) occurring in rhizospheres from the areas of former and contemporary Zn-Pb ore mining. Min. Sci. 2015, 22, 125–138. [Google Scholar] [CrossRef]
- Kicińska, A.; Gruszecka-Kosowska, A. Long-term changes of metal contents in two metallophyte species (Olkusz area of Zn-Pb ores, Poland). Environ. Monit. Assess. 2016, 188, 339. [Google Scholar] [CrossRef] [PubMed]
- Pope, C.A.; Ezzati, M.; Dockery, D.W. Fine-particulate air pollution and life expectancy in the United States. N. Engl. J. Med. 2009, 360, 376–386. [Google Scholar] [CrossRef]
- Brunekreef, B.; Forsberg, B. Epidemiological evidence of effects of coarse airborne particles on health. Eur. Respir. J. 2005, 26, 309–318. [Google Scholar] [CrossRef] [PubMed]
- Mills, A.; Le Hunte, S. An Overview of Semiconductor Photocatalysis. J. Photochem. Photobiol. A Chem. 1997, 108, 1–35. [Google Scholar] [CrossRef]
- Wang, D.; Leng, Z.; Yu, H.; Hüben, M.; Kollmann, J.; Oese, M. Durability of epoxy-bonded TiO2-modified aggregate as a photocatalytic coating layer form asphalt pavement under vehicle tire polishing. Wear 2017, 382–383, 1–7. [Google Scholar] [CrossRef]
- Morillas, H.; Marcaida, I.; Maguregui, M.; Upasen, S.; Gallego-Cartagena, E.; Madariaga, J.M. Identification of metals and metalloids as hazardous elements in PM2.5 and PM10 collected in a coastal environment affected by diffuse contamination. J. Clean. Prod. 2019, 226, 369–378. [Google Scholar] [CrossRef]
- Boggs, S., Jr. Petrology of Sedimentary Rocks, 2nd ed.; Cambridge University Press: London, UK, 2009; 600p. [Google Scholar] [CrossRef]
- Stanienda, K. Fazy mineralne w skałach węglanowych warstw gogolińskich obszaru Śląska Opolskiego. (Mineral Phases in Carbonate Rocks of the Gogolin Beds from the Area of Opole Silesia). Gospod. Surowcami Miner.–Miner. Resour. Manag. 2014, 30, 17–42, (In Polish with English Abstract). [Google Scholar] [CrossRef]
- Jabłońska, M.; Rietmeijer, F.J.M.; Janeczek, J. Fine-grained barite in coal fly ash from the Upper Silesian industrial region. Environ. Geol. 2001, 40, 941–948. [Google Scholar] [CrossRef]
- Gázquez, F.; Rull, F.; Medina, J.; Sanz-Arranz, A.; Sanz, C. Linking groundwater pollution to the decay of 15th-century sculptures in Burgos Cathedral (northern Spain). Environ. Sci. Pollut. Res. 2015, 22, 15677–15689. [Google Scholar] [CrossRef]
- Benavente, D.; de Jongh, M.; Cañaveras, J.C. Weathering Processes and Mechanisms Caused by Capillary Waters and Pigeon Droppings on Porous Limestones. Minerals 2021, 11, 18. [Google Scholar] [CrossRef]
- Coletti, C.; Cesareo, L.P.; Nava, J.; Germinario, L.; Maritan, L.; Massironi, M.; Mazzoli, C. Deterioration Effects on Bricks Masonry in the Venice Lagoon Cultural Heritage: Study of the Main Façade of the Santa Maria dei Servi Church (14th Century). Heritage 2023, 6, 1277–1292. [Google Scholar] [CrossRef]
Analysed Point * | |||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Element | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 |
C | 5.98 | 7.47 | 5.66 | 5.43 | 26.52 | 25.96 | 5.22 | 4.03 | 5.51 | 4.16 | 69.79 | 50.84 | 4.77 | 4.73 | 4.58 |
O | 41.11 | 38.84 | 34.24 | 45.51 | 41.78 | 32.37 | 37.51 | 40.59 | 18.96 | 36.81 | 20.20 | 16.14 | 47.00 | 43.92 | 40.27 |
Na | b.d.l. | b.d.l. | b.d.l. | 0.69 | 0.39 | b.d.l. | b.d.l. | 0.24 | 0.19 | b.d.l. | 0.28 | b.d.l. | b.d.l. | b.d.l. | b.d.l |
Mg | 3.30 | 0.98 | 1.12 | 1.22 | 0.58 | 0.24 | 0.56 | 1.81 | 0.77 | 1.20 | 0.21 | b.d.l. | 2.56 | 0.49 | 0.51 |
Al | 5.49 | 2.37 | 2.45 | 14.74 | 10.94 | 6.47 | 1.44 | 1.86 | 1.79 | 1.96 | 0.64 | b.d.l. | 2.28 | 1.19 | 1.35 |
Si | 6.09 | 3.44 | 3.49 | 23.50 | 12.24 | 10.88 | 3.31 | 2.61 | 2.81 | 3.55 | 1.14 | 0.92 | 7.59 | 2.12 | 2.66 |
P | 0.34 | b.d.l. | 0.29 | b.d.l. | b.d.l. | b.d.l. | b.d.l. | 0.l8 | b.d.l. | 0.33 | b.d.l. | b.d.l. | 0.60 | b.d.l. | b.d.l. |
S | 2.03 | 9.73 | 2.17 | 0.89 | 1.62 | 1.82 | 1.86 | 3.10 | 6.79 | 3.55 | 2.71 | 2.83 | 4.78 | 6.60 | 6.65 |
Cl | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. |
K | 0.49 | 0.50 | 0.47 | 2.89 | 1.28 | 2.03 | 0.45 | 0.23 | 0.57 | 0.42 | 0.77 | b.d.l. | 0.73 | 0.33 | 0.41 |
Ca | 2.77 | 2.66 | 2.60 | 1.93 | 3.65 | 3.85 | 2.96 | 4.62 | 8.37 | 5.79 | 3.19 | 3.71 | 9.04 | 7.67 | 7.06 |
Ba | b.d.l. | 29.02 | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. |
Ti | 0.59 | b.d.l. | b.d.l. | 0.51 | 0.34 | b.d.l. | b.d.l. | 0.13 | 0.38 | b.d.l. | b.d.l. | b.d.l. | 0.56 | b.d.l. | 0.32 |
Cr | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | 0.64 | b.d.l | 26.77 | b.d.l. | b.d.l. | b.d.l. | 0.50 | b.d.l. | 0.22 |
Mn | 0.61 | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | 0.71 | 0.91 | 0.59 | b.d.l. | b.d.l. | 3.17 | b.d.l. | 0.17 |
Fe | 31.21 | 4.97 | 47.64 | 2.63 | 0.69 | 0.85 | 46.04 | 39.90 | 26.10 | 40.67 | 1.06 | 6.29 | 14.26 | 31.77 | 33.54 |
Co | b.d.l. | b.d.l | b.d.l | b.d.l | b.d.l | b.d.l | b.d.l | b.d.l | b.d.l | b.d.l | b.d.l | 0.17 | b.d.l. | b.d.l. | b.d.l |
Cu | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | 0.32 | b.d.l. | b.d.l | b.d.l. | b.d.l. | b.d.l. | b.d.l. | 1.15 | 1.17 | 1.41 |
Zn | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | 3.53 | b.d.l. | b.d.l | b.d.l. | 0.98 | b.d.l. | b.d.l. | 1.01 | b.d.l. | 0.79 |
As | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l | b.d.l. | b.d.l. | b.d.l. | 19.11 | b.d.l. | b.d.l. | b.d.l. |
Pb | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | 11.42 | b.d.l. | b.d.l | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. | b.d.l. |
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Marszałek, M.; Dudek, K.; Gaweł, A. Black Crust from Historic Buildings as a Natural Indicator of Air Pollution: A Case Study of the Lipowiec Castle, Babice, Southern Poland. Sustainability 2024, 16, 3816. https://doi.org/10.3390/su16093816
Marszałek M, Dudek K, Gaweł A. Black Crust from Historic Buildings as a Natural Indicator of Air Pollution: A Case Study of the Lipowiec Castle, Babice, Southern Poland. Sustainability. 2024; 16(9):3816. https://doi.org/10.3390/su16093816
Chicago/Turabian StyleMarszałek, Mariola, Krzysztof Dudek, and Adam Gaweł. 2024. "Black Crust from Historic Buildings as a Natural Indicator of Air Pollution: A Case Study of the Lipowiec Castle, Babice, Southern Poland" Sustainability 16, no. 9: 3816. https://doi.org/10.3390/su16093816