Hostname: page-component-586b7cd67f-g8jcs Total loading time: 0 Render date: 2024-11-24T05:58:45.810Z Has data issue: false hasContentIssue false
  • English
  • Français

Microstructural and Analytical Study of Uncommon Corrosion Features on Archaeological Cu-As Alloys from Tappeh Graziani in Southeastern Iran

Published online by Cambridge University Press:  10 February 2022

Mohammad Mortazavi Open the ORCID record for Mohammad Mortazavi [Opens in a new window] ,
Hosseinali Kavosh Open the ORCID record for Hosseinali Kavosh [Opens in a new window] ,
Sogand Naghavi  and
Reza Khanjari
Mohammad Mortazavi
Affiliation:
Faculty of Conservation and Restoration, Art University of Isfahan, Isfahan, Iran
Hosseinali Kavosh*
Affiliation:
Department of Archaeology, University of Zabol, Zabol, Iran
Sogand Naghavi
Affiliation:
Department of conservation and restoration of historical artifacts, University of Zabol, Zabol, Iran
Reza Khanjari
Affiliation:
Department of conservation and restoration of historical artifacts, University of Zabol, Zabol, Iran
*
*Corresponding author: Hosseinali Kavosh, E-mail: [email protected]
Get access

Abstract

The morphology and composition of the corrosion products of archaeological arsenical copper alloys buried in a specific environment for a long time were investigated using optical microscopy (OM), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS), micro X-ray fluorescence (μ-XRF), and X-ray diffraction (XRD). The analyses demonstrated that the alloy composition of the artifacts was copper-arsenic (Cu-AS) with significant amounts of lead in some samples. Cuprite, malachite, and copper (II) hydroxychlorides were observed on a completely mineralized matrix. The surface of the objects was covered by two main corrosion layers formed on the internal cuprous oxide. However, several successive layers of corrosion products were recognized on the artifacts in some cases. Furthermore, phosphatic corrosion products including, mimetite [Pb5(AsO4)3Cl], and pyromorphite [Pb5(PO4)3Cl] were identified. Conichalcite [CaCu(AsO4)](OH), which grew in the form of Liesegang rings, was also identified as a corrosion product of one of the objects. As and Pb exhibited some enrichment in the corrosion crusts of the artifacts. Environmental changes in burial conditions, particularly due to seasonal streams and consequent changes in soil corrosivity, vicinity of objects to bone material, along with the migration of alloy elements, especially lead and arsenic, can explain the morphological features of these archaeological objects.

Keywords

archaeological Cu-As alloyscorrosionmicroscopySEM-EDSTappeh Gerziani
Type
Materials Science Applications
Information
Microscopy and Microanalysis , Volume 28 , Issue 2 , April 2022 , pp. 302 - 316
Check for updates
Copyright
Copyright © The Author(s), 2022. Published by Cambridge University Press on behalf of the Microscopy Society of America

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Abu-Baker, A (2008). Investigating the corrosion and microstructure of five copper-based archaeological artefacts from Tell el-Ajjul. AICCM Bull 31(1), 87–96.CrossRefGoogle Scholar
Afonso, FS, Neto, M, Mendonça, M, Pimenta, G, Proença, L & Fonseca, I (2009). Copper corrosion in soil: Influence of chloride contents, aeration and humidity. J Solid State Electrochem 13(11), 1757–1765.CrossRefGoogle Scholar
Alberghina, MF, Barraco, R, Brai, M, Schillaci, T & Tranchina, L (2011). Integrated analytical methodologies for the study of corrosion processes in archaeological bronzes. Spectrochim Acta B At Spectrosc 66(2), 129–137.CrossRefGoogle Scholar
Artemyev, DA & Ankushev, MN (2019). Trace elements of Cu-(Fe)-sulfide inclusions in bronze age copper slags from South Urals and Kazakhstan: Ore sources and alloying additions. Minerals 9(12), 746.CrossRefGoogle Scholar
Bernard, M & Joiret, S (2009). Understanding corrosion of ancient metals for the conservation of cultural heritage. Electrochim Acta 54(22), 5199–5205.CrossRefGoogle Scholar
Boscher, LC (2016). Reconstructing the arsenical copper production process in early Bronze Age southwest Asia, Doctoral Dissertation. UCL (University College London).Google Scholar
Constantinides, I, Adriaens, A & Adams, F (2002). Surface characterization of artificial corrosion layers on copper alloy reference materials. Appl Surf Sci 189(1–2), 90–101.10.1016/S0169-4332(02)00005-3CrossRefGoogle Scholar
De Ryck, I, Pantos, E & Adriaens, A (2007). Near Eastern ancient bronze objects from Tell Beydar (NE-Syria): Insights into their corrosion. Europhys News 38(5), 29–33.CrossRefGoogle Scholar
Di Turo, F, Coletti, F & De Vito, C (2020). Investigations on alloy-burial environment interaction of archaeological bronze coins. Microchem J 157, 104882.CrossRefGoogle Scholar
Dungworth, D (2013). An experimental study of early cooper smithing techniques. In Accidental and Experimental Archaeometallurgy, Dungworth, D & Doonan, RCP (Eds.), pp. 149–152. London: Historical Metallurgical Society.Google Scholar
Dussubieux, L, Deraisme, A, Frot, G, Stevenson, C, Creech, A & Bienvenu, Y (2008). LA–ICP–MS, SEM–EDS and EPMA analysis of eastern north American copper-based artefacts: Impact of corrosion and heterogeneity on the reliability of the LA–ICP–MS compositional results. Archaeometry 50(4), 643–657.CrossRefGoogle Scholar
El-Rehiem, F & Abd El-Rahman, M (2008). Removal of colouring materials from Egyptian albite ore. Miner Process Extr Metall 117(3), 171–174.10.1179/174328508X272371CrossRefGoogle Scholar
Fan, X (2019). Characteristics of mimetite (Pb5(AsO4)3Cl)-pyromorphite (Pb5(PO4)3Cl) corrosion products on Han Dynasty bronzes from Chongqing, China. Microchem J 149, 104062.CrossRefGoogle Scholar
Fan, X & Freestone, IC (2017). Occurrence of phosphatic corrosion products on bronze swords of the warring states period buried at Lijiaba site in Chongqing, China. Heritage Sci 5(1), 1–9.CrossRefGoogle Scholar
Fan, X, Wang, Q & Wang, Y (2020). Non-destructive in situ Raman spectroscopic investigation of corrosion products on the bronze dagger-axes from Yujiaba site in Chongqing, China. Archaeological and Anthropological Sciences 12(4), 1–10.CrossRefGoogle Scholar
Fan, X, Zhao, X, He, B & Yuan, Q (2019). Analysis of corrosion products on bronze artifacts dated to western Han dynasty unearthed in Zhuanwaxi site, Shizhu county, Chongqing. Corros Sci Protect Technol 31(1), 65–71.Google Scholar
Figueiredo, E, Araújo, M, Silva, RJ & Sennamartinez, J (2007). Corrosion of bronze alloy with some lead content: implications in the archaeometallurgical study of Late Bronze Age metal artefacts from “Fraga dos Corvos” (North Portugal). Metal 07, (ICOM-CC) Proceedings, Amsterdam 1, pp. 61–66.Google Scholar
Frame, LD (2007). Metal finds from Godin Tepe, Iran: Production, consumption, and trade. MS Thesis, Department of Materials Science and Engineering, University of Arizona.Google Scholar
Georgakopoulou, M, Bassiakos, Y & Philaniotou, O (2011). Seriphos surfaces: A study of copper slag heaps and copper sources in the context of Early Bronze Age Aegean metal production. Archaeometry 53(1), 123–145.CrossRefGoogle Scholar
Ghoniem, M (2011). The characterization of a corroded Egyptian bronze statue and a study of the degradation phenomena. Int J Conserv Sci 2(2), 95–108.Google Scholar
Hajjari, E, Oudbashi, O & Hemati Azandaryani, E (2021). Technical studies on the mechanisms of corrosion and state of conservation of two hoards of Persian copper coins (folus) from the safavid period in Iran. Journal of the Institute of Conservation 44(2), 1–13.10.1080/19455224.2021.1914698CrossRefGoogle Scholar
Hamzeh, MA, Mahmudy-Gharaie, MH, Alizadeh-Lahijani, H, Moussavi-Harami, R, Djamali, M & Naderi-Beni, A (2016). Paleolimnology of Lake Hamoun (E Iran): Implication for past climate changes and possible impacts on human settlements. Palaios 31(12), 616–629.CrossRefGoogle Scholar
Hauptmann, A, Rehren, T & Schmitt-Strecker, S (2003). Early Bronze Age copper metallurgy at Shahr-i Sokhta (Iran), reconsidered. In Man and Mining (Mensch und Bergbau). Studies in Honour of Gerd Weisgerber. Stoellner T, Koerlin G, Steffens G & Cierny J (Eds.), pp. 197–213. Bochum: Der Anchnitt Beith.Google Scholar
Holakooei, P, Oudbashi, O, Mortazavi, M & Ferretti, M (2021). On, under and beneath the patina: Evaluation of micro energy dispersive X-ray fluorescence quantitative data on the classification of archaeological copper alloys. Spectrochim ACTA B 178, 106–128.CrossRefGoogle Scholar
Ibrahim, AGAA & Maher, MA (2018). A case study of copper-arsenic ewer from the Egyptian museum in Cairo, Egypt. J Gen Union Arab Archaeol 3(3), 1–25.Google Scholar
Ingo, GM, de Caro, T, Riccucci, C & Khosroff, S (2006a). Uncommon corrosion phenomena of archaeological bronze alloys. Appl Phys A 83(4), 581–588.CrossRefGoogle Scholar
Ingo, GM, De Caro, T, Riccucci, C, Angelini, E, Grassini, S, Balbi, S, Bernardini, P, Salvi, D, Bousselmi, L, Çilingiro_glu, A, Gener, M, Gouda, VK, Al Jarrah, O, Knosroff, S, Mahdjoub, Z, Al Saad, Z, El-Saddik, W & Vassiliou, P (2006b). Large scale investigation of chemical composition, structure and corrosion mechanism of bronze archaeological artefacts from Mediterranean basin. Appl Phys A 83(4), 513–520.CrossRefGoogle Scholar
Kampf, AR, Steele, IM & Jenkins, RA (2006). Phosphohedyphane, Ca2Pb3(PO4)3Cl, the phosphate analog of hedyphane: Description and crystal structure. Am Mineral 91(11–12), 1909–1917.CrossRefGoogle Scholar
Kavosh, HA (2010). Primary Report of the First Season of Excavation in Graziani Site. Sistan. Archived in Center of Sistan and Baluchistan Documentation of Cultural Heritage, Handicrafts and Tourism Organization. Unpublished manuscript. (in persian).Google Scholar
Kavosh, HA, Vidale, M & Nashli, HF (2019a). Introduction. In Prehistoric Sistan 2, Tappeh Graziani, Sistan, Iran: Stratigraphy, Formation Processes and Chronology of a Suburban Site of Shahr-i Sokhta, Rossi, AV (Ed.), pp. 7–10. ISMEO, Roma: University of Padova, Antilia.Google Scholar
Kavosh, HA, Vidale, M & Nashli, HF (2019b). The site and the recent excavations. In Prehistoric Sistan 2, Tappeh Graziani, Sistan, Iran: Stratigraphy, Formation Processes and Chronology of a Suburban Site of Shahr-i Sokhta, Rossi, AV (Ed.), pp. 25–98. ISMEO, Roma: University of Padova, Antilia.Google Scholar
Kavosh, HA, Vidale, M & Nashli, HF (2019c). Small finds and particular artefacts. In Prehistoric Sistan 2, Tappeh Graziani, Sistan, Iran: Stratigraphy, Formation Processes and Chronology of a Suburban Site of Shahr-i Sokhta, Rossi, AV (Ed.), pp. 155–171. ISMEO, Roma: University of Padova, Antilia.Google Scholar
Kmošek, J, Odler, M, Jamborová, T, Msallamová, S, S̆álková, K & Kmoníčková, M (2016). Archaeometallurgical study of copper alloy tools and model tools from the Old kingdom necropolis at giza. In Old Kingdom Copper Tools and Model Tools Archaeopress, Older, M (Ed.), pp. 238–248. Oxford: Archaeopress.Google Scholar
Luo, W, Jin, R, Qin, Y, Huang, F & Wang, C (2010). Analysis of the corrosion products of the ancient bronzes excavated from Qiaojiayuan tombs. Appl Phys Res 2(2), 156–169.Google Scholar
MacLeod, ID (1981). Bronze disease: An electrochemical explanation. ICCM Bull 7(1), 16–26.CrossRefGoogle Scholar
Mashkour, M, Fathi, H, Davoudi, H & Kavosh, HA (2019). Animals remains from Tappeh Graziani. In Prehistoric Sistan 2, Tappeh Graziani, Sistan, Iran: Stratigraphy, Formation Processes and Chronology of a Suburban Site of Shahr-I Sokhta, Rossi, AV (Ed.), pp. 173–186. ISMEO, Roma: University of Padova, Antilia.Google Scholar
McKerrell, H & Tylecote, RF (1972). The working of copper-arsenic alloys in the Early Bronze Age and the effect on the determination of provenance. Proc Prehist Soc 38, 209–218.CrossRefGoogle Scholar
Megahed, MM (2014). A comparative characterization and practical study of bronze patinas and corrosion mechanism, applied on some ancient objects from Egypt and Yemen. Int J Conserv Sci 5(2), 161–176.Google Scholar
Mezzi, A, De Caro, T, Riccucci, C, Faraldi, F, Veroli, C & Caschera, D (2013). Unusual surface degradation products grown on archaeological bronze artefacts. Appl Phys A 113(4), 1121–1128.CrossRefGoogle Scholar
Mödlinger, M, de Oro Calderon, R & Haubner, R (2019). Arsenic loss during metallurgical processing of arsenical bronze. Archaeol Anthropol Sci 11(1), 133–140.CrossRefGoogle Scholar
Mortazavi, M (2013). Cleaning principle of ancient Bronze artefacts based on recognition of Cuprite as original surface and evaluation of its methods. Art University of Isfahan.Google Scholar
Mutin, B & Minc, L (2019). The formative phase of the Helmand civilization, Iran and Afghanistan: New data from compositional analysis of ceramics from Shahr-i Sokhta, Iran. J Archaeol Sci Rep 23, 881–899.Google Scholar
Nord, A, Mattsson, E & Tronner, K (2005). Factors influencing the long-term corrosion of bronze artefacts in soil. Prot Met 41(4), 309–316.CrossRefGoogle Scholar
Nørgaard, HW (2017). Portable XRF on prehistoric bronze artefacts: Limitations and use for the detection of bronze age metal workshops. Open Archaeol 3(1), 101–122.Google Scholar
Ottaway, BS (2001). Innovation, production and specialization in early prehistoric copper metallurgy. Eur J Archaeol 4(1), 87–112.10.1179/eja.2001.4.1.87CrossRefGoogle Scholar
Oudbashi, O (2015). Multianalytical study of corrosion layers in some archaeological copper alloy artefacts. Surf Interface Anal 47(13), 1133–1147.CrossRefGoogle Scholar
Pasero, M, Kampf, AR, Ferraris, C, Pekov, IV, Rakovan, J & White, TJ (2010). Nomenclature of the apatite supergroup minerals. Eur J Mineral 22(2), 163–179.CrossRefGoogle Scholar
Piccardo, P, Mille, B & Robbiola, L (2007). Tin and copper oxides in corroded archaeological bronzes. In Corrosion of Metallic Heritage Artefacts, Dillmann, P, Béranger, G, Piccardo, P & Matthiesen, H (Eds.), pp. 239–262. Cambridge: Woodhead Publishing Limited.CrossRefGoogle Scholar
Pinasco, MR, Ienco, MG, Piccardo, P, Pellati, G & Stagno, E (2007). Metallographic approach to the investigation of metallic archaeological objects. Ann Chim 97(7), 553–574.CrossRefGoogle Scholar
Pronti, L, Felici, AC, Alesiani, M, Tarquini, O, Bracciale, MP, Santarelli, ML, Pardini, G & Piacentini, M (2015). Characterisation of corrosion layers formed under burial environment of copper-based Greek and roman coins from pompeii. Appl Phys A 121(1), 59–68.CrossRefGoogle Scholar
Quaranta, M, Catelli, E, Prati, S, Sciutto, G & Mazzeo, R (2014). Chinese archaeological artefacts: Microstructure and corrosion behaviour of high-leaded bronzes. J Cult Herit 15(3), 283–291.CrossRefGoogle Scholar
Reddy, BJ, Frost, RL & Martens, WN (2005). Characterisation of conichalcite by SEM, FTIR, Raman and electronic reflectance spectroscopy. Mineral Mag 61(8), 1721–1728.Google Scholar
Rehren, T & Northover, J (1991). Selenium and tellurium in ancient copper ingots. In Proceedings of the 27th Symposium on Archaeometry, Heidelberg, Pernicka E & Wagner GA (Eds.), pp. 221–228. Basel, Boston, Berlin: Birkhäuser Verlag.Google Scholar
Robbiola, L, Blengino, J-M & Fiaud, C (1998). Morphology and mechanisms of formation of natural patinas on archaeological Cu–Sn alloys. Corros Sci 40(12), 2083–2111.CrossRefGoogle Scholar
Robbiola, L, Fiaud, C & Harch, A (1993). Characterisation of passive layers of Bronze patinas (Cu-Sn alloys) in relation with the tin content of the alloy. In Eur. Symp. Modif. Passiv. Film, Marcus P, Baroux B & Keddam M (Eds.), pp. 150–154. France: The Institute of Materials.Google Scholar
Robbiola, L & Hurtel, L-P (1995). Standard nature of the passive layers of buried archaeological Bronze the example of two Roman half-length portraits. In METAL 95: International Conference on Metals Conservation, MacLeod I, Pennec S & Robbiola L (Eds.), pp. 109–117. London: James and James Science Publisher.Google Scholar
Robbiola, L & Portier, R (2006). A global approach to the authentication of ancient bronzes based on the characterization of the alloy–patina–environment system. J Cult Herit 7(1), 1–12.CrossRefGoogle Scholar
Sajjadi, S, Foruzanfar, F, Shirazi, R & Baghestani, S (2003). Excavations at Shahr-i Sokhta first preliminary report on the excavations of the graveyard, 1997–2000. Iran 41(1), 21–97.CrossRefGoogle Scholar
Sakai, S, Yoshiasa, A, Sugiyama, K & Miyawaki, R (2009). Crystal structure and chemistry of conichalcite, CaCu (AsO4)(OH). J Mineral Petrol Sci 104, 125–131.10.2465/jmps.080430CrossRefGoogle Scholar
Sandu, I, Mircea, O, Sandu, IG & Vasilache, V (2013). The liesegang effect on ancient bronze items discovered in Romania. Int J Conserv Sci 4(IS), 573–586.Google Scholar
Schweizer, F (1994). Bronze objects from lake sites: From patina to “biography”. In Ancient and Historic Metals, Scott, DA, Podany, J & Considine, BB (Eds.), pp. 33–50. USA: Conservation and Scientific Research, Getty Museum and the Getty Conservation Institute.Google Scholar
Scott, DA (1985). Periodic corrosion phenomena in bronze antiquities. Stud Conserv 30(2), 49–57.Google Scholar
Scott, DA (1990). Bronze disease: A review of some chemical problems and the role of relative humidity. JAIC 29(2), 193–206.Google Scholar
Scott, DA (1991). Metallography and Microstructure in Ancient and Historic Metals. Los Angeles, California: Getty Publications, US.Google Scholar
Scott, DA (2002). Copper and Bronze in Art: Corrosion, Colorants, Conservation. Los Angeles, California: Getty Publications, US.Google Scholar
Scott, DA & Schwab, R (2019). Metallography in Archaeology and Art: Cultural Heritage Science. Cham, Switzerland: Springer.CrossRefGoogle Scholar
Shevade, AV, Erickson, L, Pierzynski, G & Jiang, S (2001). Formation and stability of substituted pyromorphite: A molecular modeling study. J Hazard Subst Res 3, 1–12.Google Scholar
Soffritti, C, Fabbri, E, Merlin, M, Garagnani, GL & Monticelli, C (2014). On the degradation factors of an archaeological bronze bowl belonging to a private collection. Appl Surf Sci 313, 762–770.CrossRefGoogle Scholar
Srivastava, A & Balasubramaniam, R (2005). Microstructural characterization of copper corrosion in aqueous and soil environments. Mater Charact 55(2), 127–135.CrossRefGoogle Scholar
Thornton, C & Lamberg-Karlovsky, C (2004). A new look at the prehistoric metallurgy of southeastern Iran. Iran 42(1), 47–59.CrossRefGoogle Scholar
Thornton, CP (2009). The emergence of complex metallurgy on the Iranian plateau: Escaping the levantine paradigm. J World Prehist 22(3), 301–327.CrossRefGoogle Scholar
Thornton, CP (2010). The rise of arsenical copper in southeastern Iran. Iran Antiq 45, 31–50.CrossRefGoogle Scholar
Zhang, X (2002). An unusual corrosion product, pyromorphite, from a bronze An: A technical note. Stud Conserv 47(1), 76–79.Google Scholar