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Prescreening Hydraulic Lime-Binders for Disordered Calcite in Caesarea Maritima: Characterizing the Chemical Environment Using FTIR

Published online by Cambridge University Press:  20 April 2020

Yotam Asscher Open the ORCID record for Yotam Asscher [Opens in a new window] ,
Aliza van Zuiden ,
Chen Elimelech ,
Peter Gendelman ,
Uzi ‘Ad ,
Jacob Sharvit ,
Michele Secco ,
Giulia Ricci Open the ORCID record for Giulia Ricci [Opens in a new window]  and
Gilberto Artioli
Yotam Asscher*
Affiliation:
Israel Antiquities Authority, Jerusalem, Israel
Aliza van Zuiden
Affiliation:
Israel Antiquities Authority, Jerusalem, Israel
Chen Elimelech
Affiliation:
Israel Antiquities Authority, Jerusalem, Israel
Peter Gendelman
Affiliation:
Israel Antiquities Authority, Jerusalem, Israel
Uzi ‘Ad
Affiliation:
Israel Antiquities Authority, Jerusalem, Israel
Jacob Sharvit
Affiliation:
Israel Antiquities Authority, Jerusalem, Israel
Michele Secco
Affiliation:
Inter-Departmental Research Center for the Study of Cement Materials and Hydraulic Binders (CIRCe), University of Padova, Italy Department of Cultural Heritage (DBC), University of Padova, Italy
Giulia Ricci
Affiliation:
Inter-Departmental Research Center for the Study of Cement Materials and Hydraulic Binders (CIRCe), University of Padova, Italy Department of Geosciences, University of Padova, Italy
Gilberto Artioli
Affiliation:
Inter-Departmental Research Center for the Study of Cement Materials and Hydraulic Binders (CIRCe), University of Padova, Italy Department of Geosciences, University of Padova, Italy
*
*Corresponding author. Email: yotam.asscher@gmail.com.
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Abstract

Hydraulic lime binders are considered a technological marvel which revolutionized construction techniques in antiquity. The core material is made of a binder that is a mixture of calcite and hydraulic phases, which are amorphous silicate compounds that nanostructurally polymerize into insoluble phases that harden even underwater, formed during the reaction between lime and reactive silicates such as volcanic ash. This is also what makes hydraulic lime so hard to radiocarbon (14C) date. These insoluble phases contain carbonates that may set centuries following their application, resulting in younger ages, which may contaminate the calcite fraction that is favorable for 14C dating. This calcite fraction forms upon the incorporation of atmospheric carbon dioxide during the setting of the hydrated lime. Therefore, different characterization methods are being constantly developed for identifying and characterizing the components of hydraulic lime-binders. In this work, we present a rapid characterization technique based on Fourier transform infrared spectroscopy (FTIR) that characterizes the atomic disorder and chemical environment of the carbonates and silicates fractions in the binder. The atomic disorder of the calcite crystallites was determined by the ν2 and ν4 vibrational modes, and the silicates were characterized by the main peak asymmetry and full width at half maximum (FWHM). Different hydraulic binders from Caesarea Maritima were examined, including Herodian mortars from the underwater breakwater and on-land plasters and mortars from the portʼs warehouse and vaults. Hydraulic binders, in which the calcite fraction in the binder shows atomic disorder that is comparable to modern plaster binders, was associated with silicates that have asymmetry and FWHM of clays and quartz. These materials are considered to be in good preservation state for 14C dating since their carbonates crystallites are disordered and did not interact with the environment chemically to form stable and ordered crystals. Interestingly, the atomic disorder of binders that underwent chemical alterations and recrystallization processes, are associated with reactive silicates aggregates such as volcanic ash (pozzolana). These results suggest a new way to prescreen materials for radiocarbon dating based on the composition of lime-binders and preservation state of the carbonate fraction and hydraulic products.

Keywords

atomic disorderFTIRgrinding curveshydraulic lime-builders
Type
Research Article
Information
Radiocarbon , Volume 62 , Issue 3: MoDIM 2018 Proceedings of the Mortar Dating International Meeting , June 2020 , pp. 527 - 543
Copyright
© 2020 by the Arizona Board of Regents on behalf of the University of Arizona

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Footnotes

Selected Papers from the Mortar Dating International Meeting, Pessac, France, 25–27 Oct. 2018

References

REFERENCES

‘Ad, U, Arbel, Y, Gendelman, P. 2018. Caesarea, Area LL. HA-ESI 130 (July 16). http://www.hadashot-esi.org.il/report_detail_eng.aspx?id=25450&mag_id=126 [accessed July 31, 2019].Google Scholar
Addis, A, Secco, M, Marzaioli, F, Artioli, G, Arnau, AC, Passariello, I, Terrasi, F, Brogiolo, GP. 2019. Selecting the most reliable 14C dating material inside mortars: The origin of the Padua Cathedral. Radiocarbon. 61(2):375–393. doi: 10.1017/RDC.2018.147.CrossRefGoogle Scholar
Artioli, G. 2010. Scientific methods and cultural heritage. Oxford University Press.CrossRefGoogle ScholarPubMed
Artioli, G, Secco, M, Addis, A, Bellotto, M. 2017. Role of hydrotalcite-type layered double hydroxides in delayed pozzolanic reactions and their bearing on mortar dating: composition, properties, application. In: Herbert, P, editor. Cementitious materials: composition, properties, application. Berlin: Walter de Gruyter GmbH. 500 p.Google Scholar
Asscher, Y, Weiner, S, Boaretto, E. 2011a. Variations in atomic disorder in biogenic carbonate hydroxyapatite using the Infrared spectrum grinding curve method. Advanced Functional Materials, 21(17):3308–3313.10.1002/adfm.201100266CrossRefGoogle Scholar
Asscher, Y, Regev, L, Weiner, S, Boaretto, E. 2011b. Atomic disorder in fossil tooth and bone mineral: an FTIR study using the grinding curve method. Archaeoscience 35:135–141.CrossRefGoogle Scholar
Asscher, Y, Dal Sasso, G, Nodari, L, Angelini, I, Ballaran, TB, Artioli, G. 2017. Differentiating between long and short range disorder in infra-red spectra: on the meaning of “crystallinity” in silica. Physical Chemistry Chemical Physics 19(32):21783–21790.CrossRefGoogle ScholarPubMed
Boynton, RS. 1980. Chemistry and technology of lime and limestone. New York: John Wiley & Sons, Inc.Google Scholar
Brandon, CJ, Hohlfelder, RL, Jackson, MD, Oleson, JP, editors. 2014. Building for eternity: The history and technology of Roman concrete engineering in the sea. Oxford: Oxbow Books.CrossRefGoogle Scholar
Brangule, A, Gross, KA. 2015. Importance of FTIR spectra deconvolution for the analysis of amorphous calcium phosphates. IOP Conf. Ser. Mater. Sci. Eng. 77: 012027.CrossRefGoogle Scholar
Chu, V, Regev, L, Weiner, S, Boaretto, E. 2008. Differentiating between anthropogenic calcite in plaster, ash and natural calcite using infrared spectroscopy: implications in archaeology. Journal of Archaeological Science 35:905–e911.CrossRefGoogle Scholar
Conterosito, E, Gianotti, V, Palin, L, Boccaleri, E, Viterbo, D, Milanesio, M. 2018. Facile preparation methods of hydrotalcite layered materials and their structural characterization by combined techniques. Inorganica Chim Acta. 470:36–50. doi: 10.1016/j.ica.2017.08.007.CrossRefGoogle Scholar
Delibrias, G, Labeyrie, J. 1964. Dating of old mortars by the carbon-14 method. Nature 201.CrossRefGoogle Scholar
Dollase, WA. 1986. Correction of intensities for preferred orientation in powder diffractometry: application of the March model. Journal of Applied Crystallography 19:267–72.CrossRefGoogle Scholar
Farmer, VC. 1974. The infrared spectra of minerals. London: Mineralogical Society.CrossRefGoogle Scholar
Folk, RL, Valastro, S. 1976. Successful technique for dating of lime mortar by Carbon-14. Journal of Field Archaeology 3(2):203–208.CrossRefGoogle Scholar
Hajdas, I, Lindroos, A, Heinemeier, J, Ringbom, Å, Marzaioli, F, Terrasi, F, Passariello, I, Capano, M, Artioli, G, Addis, A, et al. 2017. Preparation and dating of mortar samples—Mortar Dating Intercomparison Study (MODIS). Radiocarbon 59(5):1–14.CrossRefGoogle Scholar
Hayen, R, Van Strydonck, M, Fontaine, L, Boudin, M, Lindroos, A, Heinemeier, J, Ringbom, Å, Michalska, D, Hajdas, I, Hueglin, S, et al. 2017. Mortar dating methodology: Assessing recurrent issues and needs for future research. Radiocarbon 59(6):1859–71.CrossRefGoogle Scholar
Heinemeier, J, Jungner, H, Lindroos, A, Ringbom, Å, von Konow, T, Rud, N. 1997. AMS 14C dating of lime mortar. Nuclear Instruments and Methods in Physics Research B 123:487–495.10.1016/S0168-583X(96)00705-7CrossRefGoogle Scholar
Heinemeier, J, Ringbom, Å, Lindroos, A, Sveinbjörnsdóttir, ÁE. 2010. Successful AMS 14C Dating of Non–Hydraulic Lime Mortars from the Medieval Churches of the Åland Islands, Finland. Radiocarbon. 52(1):171–204.10.1017/S0033822200045124CrossRefGoogle Scholar
Holum, KG. 2008. Caesarea. The combined Caesarea Expedition excavations. In: Stern, E, Geva, H, Paris, A, editors. The new encyclopedia of archaeological excavations in the Holy Land. Supplement Vol. 5. Jerusalem. p. 1665–1668.Google Scholar
Jackson, M. 2014. Sea-water concretes and their material characteristics. In: Building for eternity. Oxford: Oxbow Books. p. 141–187.CrossRefGoogle Scholar
Jackson, MD, Mulcahy, SR, Chen, H, Li, Y, Li, Q, Cappelletti, P, Wenk, HR. 2017. Phillipsite and Al-tobermorite mineral cements produced through low-temperature water-rock reactions in Roman marine concrete. Am Mineral. 102(7):1435–1450. doi: 10.2138/am–2017–5993CCBY.CrossRefGoogle Scholar
Lindroos, A, Heinemeier, J, Ringbom, Å, Braskèn, M, Sveinbjörnsdóttir, Á. 2007. Mortar dating using AMS 14C and sequential dissolution: examples from medieval, non-hydraulic lime mortars from the Aland Island, SW Finland. Radiocarbon 49(1):47–67.10.1017/S0033822200041898CrossRefGoogle Scholar
Marzaioli, F, Lubritto, C, Nonni, S, Passariello, I, Capano, M, Ottaviano, L, Terrasi, F. 2014. Characterisation of a new protocol for mortar dating: 14C evidences. Open Journal of Archaeometry 2(2):55–59.CrossRefGoogle Scholar
Michalska, D. 2019. Influence of different pretreatments on mortar dating results. Nuclear Instruments and Methods in Physics Research B 456:236–246.CrossRefGoogle Scholar
Michalska, D, Czernik, J. 2015. Carbonates in leaching reactions in context of 14C dating. Nuclear Instruments and Methods in Physics Research B 361:431–439. doi: 10.1016/j.nimb.2015.08.033.CrossRefGoogle Scholar
Miriello, D, Barca, D, Bloise, A, Ciarallo, A, Crisci, GM, De Rose, T, Gattuso, C, Gazineo, F, La Russa, MF. 2010. Characterisation of archaeological mortars from Pompeii (Campania, Italy) and identification of construction phases by compositional data analysis. Journal of Archaeological Science 37(9):2207–2223. doi: 10.1016/j.jas.2010.03.019.CrossRefGoogle Scholar
Nawrocka, D, Michniewicz, J, Pawlyta, J. 2005. Application of radiocarbon method for dating of lime mortars. Geochronometria 24:109–115.Google Scholar
Poduska, KM, Regev, L, Boaretto, E, Addadi, L, Weiner, S, Kronik, L, Curtarolo, S. 2011. Decoupling local disorder and optical effects in infrared spectra: differentiating between calcites with different origins. Advanced Materials 23: 550–554.10.1002/adma.201003890CrossRefGoogle ScholarPubMed
Ponce-Antón, G, Ortega, L, Zuluaga, M, Alonso-Olazabal, A, Solaun, J. 2018. Hydrotalcite and hydrocalumite in mortar binders from the medieval castle of Portilla (Álava, North Spain): accurate mineralogical control to achieve more reliable chronological ages. Minerals 8(8):326. doi: 10.3390/min8080326.CrossRefGoogle Scholar
Porath, Y. 2008. Caesarea. The Israel Antiquities Authority excavations. In: Stern, E, Geva, H, Paris, A, editors. The new encyclopedia of archaeological excavations in the Holy Land. Supplement Vol. 5. Jerusalem. p.1656–1665.Google Scholar
Raban, A. 2009. Underwater excavations in the Herodian harbor Sebastos. In: Holum, KG, Stabler, JA, Reinhard, EG, editors. Caesarea reports and studies: excavations 1995–2007 within the Old City and the Harbor. BAR International Series 1784: 129–142.Google Scholar
Reinhard, EG, Raban, A. 2009. Site formation and stratigraphic development of the ancient harbor at Caesarea Maritima, Israel. In: Holum, KG, Stabler, JA, Reinhard, EG, editors. Caesarea reports and studies: excavations 1995–2007 within the Old City and the Harbor. BAR International Series 1784:155–182.Google Scholar
Regev, L, Poduska, KM, Addadi, L, Weiner, S, Boaretto, E. 2010. Distinguishing between calcites formed by different mechanisms using infrared spectrometry: archaeological applications. Journal of Archaeological Science 37(12):3022–3029.CrossRefGoogle Scholar
Regev, L, Eckmeier, E, Mintz, E, Weiner, S, Boaretto, E. 2011. Radiocarbon concentrations of wood ash calcite: potential for dating. Radiocarbon 53(1):117–127.CrossRefGoogle Scholar
Ricci, G, Secco, M, Marzaioli, F, Terrasi, F, Passariello, I, Addis, A, Lampugnani, P, Artioli, G. 2020. The Cannero Castle (Italy): development of radiocarbon dating methodologies in the framework of the layered double hydroxide mortars. Radiocarbon 62. In this issue.CrossRefGoogle Scholar
Rietveld, H. 1969. A profile refinement method for nuclear and magnetic structures. Journal of Applied Crystallography 2:65–71.CrossRefGoogle Scholar
Ringbom, Å, Lindroos, A, Heinemeier, J, Sonck–Koota, P. 2014. 19 years of mortar dating: learning from experience. Radiocarbon 56:619–635.CrossRefGoogle Scholar
Rowe, H, Hughes, N, Robinson, K. 2012. The quantification and application of handheld energy-dispersive X-ray fluorescence (ED-XRF) in mudrock chemostratigraphy and geochemistry. Chemical Geology 324:122–131.10.1016/j.chemgeo.2011.12.023CrossRefGoogle Scholar
Secco, M, Dilaria, S, Addis, A, Bonetto, J, Artioli, G, Salvadori, M. 2018. The evolution of the Vitruvian recipes over 500 years of floor-making techniques: The case studies of the Domus delle Bestie Ferite and the Domus di Tito Macro (Aquileia, Italy). Archaeometry 60(2):185–206. doi: 10.1111/arcm.12305.CrossRefGoogle Scholar
Snellings, R, Mertens, G, Elsen, J. 2012. Supplementary cementitious materials, reviews in mineralogy and geochemistry. Appl. Mineral. Cement Concrete 74(1): 211–278.10.1515/9781501508356-008CrossRefGoogle Scholar
Sonninen, E, Jungner, H. 2001. An improvement in preparation of mortar for radiocarbon dating. Radiocarbon 43(2):271–273.10.1017/S0033822200038108CrossRefGoogle Scholar
Stabler, JA, Holum, KG, Stanley, FH Jr, Risser, M, Iamim, A. 2008. The Warehouse Quarter (Area LL) and the Temple Platform (Area TP), 1996–2000 and 2002 Seasons. In: Holum, KG, Stabler, JA, Reinhard, EG, editors. Caesarea reports and studies: excavations 1995–2007 within the Old City and the Harbor. BAR International Series 1784:1–40.Google Scholar
Suzuki, M, Dauphin, Y, Addadi, L, Weiner, S. 2011. Atomic order of aragonite crystals formed by mollusks. CrystEngComm 13(22):6780–6786.CrossRefGoogle Scholar
Toffolo, MB, Regev, L, Dubernet, S, Lefrais, Y, Boaretto, E. 2019. FTIR-based crystallinity assessment of aragonite-calcite mixtures in archaeological lime binders altered by diagenesis. Minerals 9(2):121.10.3390/min9020121CrossRefGoogle Scholar
Van Strydonck, M. 2016. Radiocarbon dating of lime mortars: A historic overview. In: 4th Historic Mortars Conference HMC2016. p. 648–655.Google Scholar
Vola, G, Gotti, E, Brandon, C, Oleson, JP, Hohlfelder, RL. 2011. Chemical, mineralogical and petrographic characterization of Roman ancient hydraulic concretes cores from Santa Liberata, Italy, and Caesarea Palestinae, Israel. Periodico di mineralogia, 80(2):317–338.Google Scholar
Zouridakis, N, Saliege, JF, Person, A, Filippakis, SE. 1987. Radiocarbon dating of mortars from ancient Greek palaces. Archaeometry 29(1):60–68.CrossRefGoogle Scholar
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