Abstract
The present work aim to study the effect of burial on the photoluminescnece (PL) spectra of white, crystalline marble surfaces and the physicochemical processes that take place at the marble—soil interface. The PL was studied by an argon ion laser beam, focused through a microscope objective onto the sample, offering a spatial resolution of 3 μm. Long-buried (time scale of 1,000 years) surfaces show a red (at 610 nm) emission due to Mn2+, which is also shown on fresh marble spectra and an additional broadband blue-green (380–530 nm) one. Electron paramagnetic resonance (EPR) spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) indicate that the latter emission originates from humate complexes. The complexes are most probably Ca-humates, the humic substances found in the soil and the divalent calcium cations released by the dissolution of marble calcite. Finally, the examination of recently (time scale of 50 years) buried surfaces shows that the blue-green emission and consequently the presence of humates in marble patinas are not affected by the soil organic matter content. Soil acidity however, is a critical factor, with a total absence of the blue-green emission at pH values lower than 6.
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References
Aguilar GM, Osendi MI (1982) Fluorescence of Mn2+ in CaCO3. J Lumin 27:365–375. doi:10.1016/0022-2313(82)90037-0
Amoroso GG, Fassina V (1983) Stone decay and conservation. Atmospheric pollution, cleaning, consolidation and protection. Elsevier, Amsterdam, pp 420–421
Ball DF (1964) Loss-on-ignition as an estimate of organic matter and organic carbon in non-calcareous soils. J Soil Sci 15:84–92. doi:10.1111/j.1365-2389.1964.tb00247.x
Bascomb CL (1974) Physical and chemical analysis of <2 mm samples. In: Avery BW, Bascomb CL (eds) Physical soil survey technical monograph 6, soil survey laboratory methods. Adlard & Son Ltd, Dorking, pp 14–42
Bryan ND, Jones DM, Appleton M, Livens FR, Jones MN, Warwick P, King K, Hall A (2000) A physicochemical model of metal–humate interactions. Phys Chem Chem Phys 2:1291–1300. doi:10.1039/a908722b
Burdon J (2001) Are the traditional concepts of the structures of humic substances realistic? Soil Sci 166:752–769. doi:10.1097/00010694-200111000-00004
Calderon T, Aguilar M, Jaque F, Coy-yll R (1984) TL from natural calcites. J Phys C Solid State Phys 17:2027–2038. doi:10.1088/0022-3719/17/11/021
Cazenave S, Chapoulie R, Villeneuve G (2003) Cathodoluminescence of synthetic and natural calcite: the effects of manganese and iron on orange emission. Mineral Petrol 78:243–253. doi:10.1007/s00710-002-0227-y
Colao F, Fantoni R, Lazic V, Morone A, Santagata A, Giardini A (2004) LIBS used as a diagnostic tool during the laser cleaning of ancient marble from Mediterranean areas. Appl Phys A 79:213–219. doi:10.1007/s00339-004-2649-3
Comelli D, Valentini G, Cubeddu R, Toniolo L (2005) Fluorescence lifetime imaging and fourier transform infrared spectroscopy of Michelangelo’s David. Appl Spectrosc 59:1174–1181. doi:10.1366/0003702055012663
De Canniere P, Joppart T, Debuist R, Dejehet F, Apers D (1985) ESR dating: a study of humic acids incorporated in synthetic calcite. Nucl Tracks 10:853–863
Garcia-Valles M, Vendrell-Saz M, Krumbein WE, Urzi C (1997) Coloured mineral coatings on monument surfaces as a result of biomineralization: the case of the Tarragona cathedral (Catalonia). Appl Geochem 12:255–266. doi:10.1016/S0883-2927(96)00057-1
Habermann D, Neuser RD, Richter DK (1998) Low limit of Mn2+-activated cathodoluminescence of calcite: state of the art. Sediment Geol 116:13–24. doi:10.1016/S0037-0738(97)00118-8
Lapuente MP, Turi B, Ph Blanc (2000) Marbles from Roman Hispania: stable isotope and cathodoluminescence characterization. Appl Geochem 15:1469–1493. doi:10.1016/S0883-2927(00)00002-0
Lasaga AC (1984) Chemical kinetics of water–rock interactions. J Geophys Res 89:4009–4025. doi:10.1029/JB089iB06p04009
Lumb MD (1978) Organic luminescence. In: Lumb MD (ed) Luminescence spectroscopy. Academic Press, New York, pp 93–148
Maravelaki-Kalaitzaki P, Anglos D, Kilikoglou V, Zafiropulos V (2001) Compositional characterization of encrustation onmarble with laser induced breakdown spectroscopy. Spectrochim Acta B 56:887–903. doi:10.1016/S0584-8547(01)00226-9
Margolis SV (1989) Authenticating ancient marble sculpture. Sci Am 260:104–110
Milori DM, Galeti HV, Martin-Neto L, Dieckow J, González-Pérez M, Bayer C, Salton J (2006) Organic matter study of whole soil samples using laser-induced fluorescence spectroscopy. Soil Sci Soc Am J 70:57–63. doi:10.2136/sssaj2004.0270
Ouatmane A, Hafidi M, El Gharous M, Revel JC (1999) Complexation of calcium ions by humic and fulvic acids. Analusis 27:428–432. doi:10.1051/analusis:1999270428
Paulenová A, Rajec P, Žemberyová M, Sasköiová G, Višacký V (2000) Strontium and calcium complexation by humic acid. J Radioanal Nucl Chem 246:623–628. doi:10.1023/A:1006727409230
Polikreti K, Christofides C (2008) Laser induced micro-photoluminescence of marble and application to authenticity testing of ancient objects. Appl Phys A 90:285–291. doi:10.1007/s00339-007-4266-4
Polikreti K, Maniatis Y (2002) A new methodology for marble provenance: investigation based on EPR spectroscopy. Archaeometry 44:1–21. doi:10.1111/1475-4754.00040
Polikreti K, Maniatis Y (2003) Micromorphology, composition and origin of the orange patina on the marble surfaces of Propylaea (Acropolis, Athens) marble surfaces. Sci Total Environ 308:111–119. doi:10.1016/S0048-9697(02)00613-7
Polikreti K, Maniatis Y (2004) Distribution changes of Mn2+ and Fe3+ on weathered marble surfaces measured by EPR spectroscopy. Atmos Environ 38:3617–3624. doi:10.1016/j.atmosenv.2004.03.048
Pouli P, Zafiropulos V, Balas C, Doganis Y, Galanos A (2003) A laser cleaning of inorganic encrustation on excavated objects: evaluation of the cleaning result by means of multi-spectral imaging. J Cult Herit 4:338 s–342 s. doi:10.1016/S1296-2074(02)01217-7
Ramseyer K, Miano TM, D’Orazio V, Wildberger A, Wagner T, Geister J (1997) Nature and origin of organic matter in carbonates from speleothems, marine cements and coral skeletons. Org Geochem 26:361–378. doi:10.1016/S0146-6380(97)00008-9
Rorimer JJ (1931) Ultraviolet rays and their use in the examination of works of art. Metropolitan Museum of Fine Arts, Boston, pp 17–23
Senesi N, Miano TM, Provenzano MR, Bruneti G (1989) Spectroscopic and compositional characterization of IHSS reference and standard fulvic and humic acids of various origin. Sci Total Environ 81/82:143–156. doi:10.1016/0048-9697(89)90120-4
Senesi N, Miano TM, Provenzano MR, Bruneti G (1991) Characterization, differentiation, and classification of humic substances by fluorescence spectroscopy. Soil Sci 152:259–271. doi:10.1097/00010694-199110000-00004
Stevenson FJ (1994) Humus chemistry. Wiley, New York
Tesoriero AJ, Pankow JF (1996) Solid solution partitioning of Sr2+, Ba2+, and Cd2+ to calcite. Geoch Cosmoch Ac 60:1053–1063. doi:10.1016/0016-7037(95)00449-1
Uesugi A, Ikeya M (2001) Electron Spin Resonance Measurement of Organic Radicals in Petroleum Source Rock Containing Transition Metal Ions. Jpn J Appl Phys 40:2251–2254. doi:10.1143/JJAP.40.2251
Ulens K, Moens L, Dams R (1990) Study of element distributions in weathered marble crusts using laser ablation inductively coupled plasma mass spectrometry. J Anal At Spectrom 9:1243–1248. doi:10.1039/ja9940901243
Van Beynen P, Bourbonniere R, Ford D, Schwarcz H (2001) Causes of colour and fluorescence in speleothems. Chem Geol 175:319–341. doi:10.1016/S0009-2541(00)00343-0
Acknowledgments
This work was supported by the Research Promotion Foundation of Cyprus (project “Authentic”). We are indebted to Dr C. Lenosis (Bio-mater Ltd., Athens, Greece) for providing unlimited access to laboratory equipment.
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Polikreti, K., Christofides, C. The role of humic substances in the formation of marble patinas under soil burial conditions. Phys Chem Minerals 36, 271–279 (2009). https://doi.org/10.1007/s00269-008-0275-x
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DOI: https://doi.org/10.1007/s00269-008-0275-x