New approach to the differentiation of marble samples using thermal analysis and chemometrics in order to identify provenance

Chemistry Central Journal

Luigi Campanella¹  Giovanni Visco¹  Mauro Tomassetti¹  Federico Marini¹  Emanuela Gregori¹  Tania Gatta¹ 

[1]Department of Chemistry, University of Rome “La Sapienza”, P.le. Aldo Moro 5, I-00185 Rome, Italy

关键词: Wyden-widmann method;    Principal component analysis;    Chemometrics;    Thermal analysis;    Marbles;   

Others  :  787776
DOI  :  10.1186/1752-153X-8-35

 received in 2013-10-22, accepted in 2014-05-20,  发布年份 2014

【 摘 要 】

Background

The possibility of applying a novel chemometric approach which could allow the differentiation of marble samples, all from different quarries located in the Mediterranean basin and frequently used in ancient times for artistic purposes, was investigated. By suggesting tentative or allowing to rule out unlikely attributions, this kind of differentiation could, indeed, be of valuable support to restorers and other professionals in the field of cultural heritage.

Experimental data were obtained only using thermal analytical techniques: Thermogravimetry (TG), Derivative Thermogravimetry (DTG) and Differential Thermal Analysis (DTA).

Results

The extraction of kinetic parameters from the curves obtained using these thermal analytical techniques allowed Activation Energy values to be evaluated together with the logarithm of the Arrhenius pre-exponential factor of the main TG-DTG process.

The main data thus obtained after subsequent chemometric evaluation (using Principal Components Analysis) have already proved useful in the identification the original quarry of a small number of archaeological marble finds.

Conclusion

One of the most evident advantages of the thermoanalytical – chemometric approach adopted seems to be that it allows the certain identification of an unknown find composed of a marble known to be present among the reference samples considered, that is, contained in the reference file. On the other hand with equal certainty it prevents the occurrence of erroneous or highly uncertain identification if the find being tested does not belong to the reference file considered.

【 授权许可】

   
2014 Gatta et al.; licensee Chemistry Central Ltd.

【 图 表 】

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【 参考文献 】

• [1]Campanella L, Gregori E, Tomassetti M, Visco G: Identification of different types of imperial age marble finds using instrumental chemical analysis and pattern recognition analysis. Ann Chem Rome 2001, 91(11–12):701-718.
• [2]Campanella L, Costanza C, Tomassetti M, Vecchio S: Kinetic processing of thermoanalytical curves of cellulose samples and assessment of possible archeometric applications. Curr Anal Chem 2010, 6(4):260-268.
• [3]Pieri M: Marmologia. Ulrico Hoepli, Milano: Dizionario di marmi e graniti italiani ed esteri. ediz; 1966.
• [4]Morbidelli P, Tucci P, Imperatori C, Polvorinos A, Preite Martinez M, Azzaro E, Hernandez MJ: Roman quarries of the Iberian peninsula: “Anasol” and “anasol-type”. Eur J Mineral 2007, 19(1):125-135.
• [5]Lazzarini L: Pietre e marmi antichi: natura, caratterizzazione, origine, storia d’uso, diffusione, collezionismo. Padova: Cedem Ed; 2004.
• [6]Ferloni P, Chierichetti A, Tomasi C, Ricci O: Marbles in the facade of the “Certosa di Pavia”: a physico-chemical study. Ann Chem Rome 2005, 95(3–4):153-159.
• [7]Kanellopoulou DG, Koutsoukos PG: The calcitic marbles/water interface: kinetic of dissolution and inhibition with potential implications in stone conservation. Langmuir 2003, 19(14):5691-5699.
• [8]Paparatti E: Note sui marmi dell’antica Roma. Acta Geoarcheologica Urbica 1990, 1(4):18-23.
• [9]Mariottini M: La Provenienza Dei Marmi Cristallini Usati In Antico: Un Problema Aperto. In Studi Miscellanei 31: Marmi Antichi, Ii Cave Tecnica Di Lavorazione Provenienze E Distribuzione. Roma: L’Erma di Bretschneider; 1998. ISBN 8870629988
• [10]Unterwurzacher M, Pollers J, Mirwald P: Provenance study of marble artefacts from the Roman burial area of Faschendorf (Carinthia, Austria). Archaeometry 2005, 47(2):265-273.
• [11]Bystritskaya EV, Pomerantsev AL, Rodionova OY: Non-linear regression analysis: new approach to traditional implementation. J Chemometr 2000, 14:667-692.
• [12]Pomerantsev AL, Rodionova OY: Hard and soft methods for prediction of antioxidants’ activity based on the DSC measurements. Chemometr Intell Lab Syst 2005, 79:73-83.
• [13]Cao R, Naya S: Nonlinear regression checking via local polynomial smoothing with applications to thermogravimetric analysis. J Chemometr 2009, 23:275-282.
• [14]Sbirrazzuoli N, Vincent L, Mija A, Guigo N: Integral, differential and advanced isoconversional methods complex mechanisms and isothermal predicted conversion–time curves. Chemometr Intell Lab Syst 2009, 96:219-226.
• [15]M Francisco-Fernández M, Tarrío-Saavedra J, Mallik A, Naya S: A comprehensive classification of wood from thermogravimetric curves. Chemometr Intell Lab Syst 2012, 118:159-172.
• [16]Marini F, Tomassetti M, Vecchio S: Detailed kinetic and chemometric study of the cellulose thermal breakdown in artificially aged and non aged commercial paper. Different methods for computing activation energy as an assessment model in archaeometric applications. Chem Cent J 2012, 6(Suppl.2):S7.
• [17]Tomassetti M, Marini F, Campanella L, Coppa A: Study of modern or ancient collagen and human fossil bones from an archaeological site of middle Nile by thermal analysis and chemometrics. Microchem J 2013, 108:7-13.
• [18]Friolo HK, Ray AS, Stuart BH, Thomas PS: Thermal analysis of heritage stones. J Therm Anal Calorim 2005, 80(3):559-563.
• [19]Bayer G, Wiedemann HG: Thermoanalytical measurements in archeometry. Thermochim Acta 1983, 69(1–2):167-173.
• [20]Jolliffe IT: Principal component analysis. 2nd edition. Heidelberg, Germany: Springer Verlag; 2002.
• [21]Engler P, Santana MW, Mittleman ML, Balazs D: Non-Isothermal, in situ XRD Analysis of dolomite decomposition. Thermochim Acta 1989, 140:67-76.
• [22]Plevova E, Kozusnikova A, Vaculikova L, Simha Martynkova G: Thermal behavior of selected Czech marble samples. J Therm Anal Calorim 2010, 101(2):657-664.
• [23]Caceres PG, Attiogbe EK: Thermal decomposition of dolomite and the extraction of its constituents. Miner Eng 1997, 10(10):1165-1176.
• [24]Samtani M, Dollimore D, Wilburn FW, Alexander K: Isolation and identification of the intermediate and final products in the thermal decomposition of dolomite in an atmosphere of carbon dioxide. Thermochim Acta 2001, 367–368:285-295.
• [25]Leiss B, Weiss T: Fabric anisotropy and its influence on physical weathering of different types of Carrara marbles. J Struct Geol 2000, 22(11–12):1737-1745.
• [26]Siegesmund S, Ullemeyer K, Weiss T, Tschegg EK: Physical weathering of marbles caused by anisotropic thermal expansion. Int J Earth Sci 2000, 89(1):170-182.
• [27]Obara B, Kozusnikova A: Utilization of the image analysis method for the detection of the morpholocical anisotropy of calcite grains in marble. Comput Geosci 2007, 11(4):275-281.
• [28]Wiedemann HG, Bayer G: Notes on the thermal decomposition of dolomite. Thermochim Acta 1987, 121:479-485.
• [29]Mc Cauley RA, Johnson LA: Decrepitation and thermal decomposition of dolomite. Thermochim Acta 1991, 185(2):271-282.
• [30]Warne SSJ: Carbonate mineral detection by variable atmosphere differential thermal analysis. Nature 1977, 269:678.
• [31]Otsuka R: Recent studies on the decomposition of the dolomite group by thermal analysis. Thermochim Acta 1986, 100(1):69-80.
• [32]Bradley WF, Burst JF, Graf PL: Crystal chemistry and differential thermal effects of dolomite. Am Mineral 1953, 38:207-217.
• [33]Visco G, Gregori E, Tomassetti M, Campanella L: Probably counterfeit in roman imperial age: pattern recognition helps diagnostic performed with inductive coupled plasma spectrometry and thermogravimetry analysis of a torso and a head of Roman age marble statue. Microchem J 2008, 88(2):210-217.
• [34]Wyden H, Widman G: Kinetic evaluation of TG measurements with multiple regression. Experientia, Supl 37 of Angew Chem Thermodyn Thermoanal 1979, 37:284-290.
• [35]Bro R, Kjeldahl K, Smilde AK, Kiers HA: Cross-validation of component models: a critical look at current methods. Anal Bioanal Chem 2008, 390(5):1241-1251.
• [36]Nomikos P, MacGregor JF: Multivariate SPC charts for monitoring batch processes. Technometrics 1995, 37(1):41-59.