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This is the peer reviewed version of the following article: A. Doménech-Carbó, M. T. Doménech-Carbó, C. Álvarez-Romero, T. Pasíes, M. Buendía, Electroanalysis 2019, 31, 1164, which has been published in final form at https://doi.org/10.1002/elan.201900090. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving., [EN] The voltammetry of immobilized particles (VIMP) was applied for grouping a series of 86 Iberian coins nominally minted in the cities of Iltirta, Castulo and Obulco in the 2(th)-1(th) BCE period for which there are no chronological data. Using characteristic signatures for the reduction of cuprite, tenorite and lead corrosion products in the patina of the coins, voltammetric grouping of coins was proposed. Voltammetric data were found to be consistent with textural and compositional properties of the surface and subsurface of selected coins using FIB-FESEM-EDX. The obtained data confirmed a clear separation between the productions of Iltirta on one side, and those of Castulo and Obulco on the other side, indicating the possibility to establish a rough chronology for these productions.

This is the peer reviewed version of the following article: Doménech Carbó, Antonio, Scholz, Fritz , Domenech Carbo, Mª Teresa, Piquero-Cilla, Juan , Montoya, Noemí, Pasies -Oviedo, Trinidad, Gozalbes, Manuel , Melchor Montserrat, José Manuel , Oliver, Arturo . (2018). Dating of Archaeological Gold by Means of Solid State Electrochemistry.ChemElectroChem, 5, 15, 2113-2117. DOI: 10.1002/celc.201800435 , which has been published in final form at http://doi.org/10.1002/celc.201800435. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving, [EN] In archaeology and history of art, age determination is a fundamental analytical problem. While several techniques for age determination of various materials, like radiocarbon dating, are established, these methods cannot be applied for metals, for which new techniques have to be developed. For the first time a dating method for archaeological gold objects is described which is based on a corrosion clock and electrochemical measurements, using the voltammetry of immobilized particles. Samples are prepared by one touch' with a graphite pencil, only transferring a few nanograms of the archaeological gold. The method has been calibrated with the help of a series of well-documented gold specimen from different prehistory museums covering the last 2600years. Our results prove that this corrosion clock is going on a constant pace, practically independent of the environment, making it most attractive for applications in archaeometry.

This is the peer reviewed version of the following article: Doménech Carbó, Antonio, Scholz, Fritz , Domenech Carbo, Mª Teresa, Piquero-Cilla, Juan , Montoya, Noemí, Pasies -Oviedo, Trinidad, Gozalbes, Manuel , Melchor Montserrat, José Manuel , Oliver, Arturo . (2018). Dating of Archaeological Gold by Means of Solid State Electrochemistry.ChemElectroChem, 5, 15, 2113-2117. DOI: 10.1002/celc.201800435 , which has been published in final form at http://doi.org/10.1002/celc.201800435. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving, [EN] In archaeology and history of art, age determination is a fundamental analytical problem. While several techniques for age determination of various materials, like radiocarbon dating, are established, these methods cannot be applied for metals, for which new techniques have to be developed. For the first time a dating method for archaeological gold objects is described which is based on a corrosion clock and electrochemical measurements, using the voltammetry of immobilized particles. Samples are prepared by one touch' with a graphite pencil, only transferring a few nanograms of the archaeological gold. The method has been calibrated with the help of a series of well-documented gold specimen from different prehistory museums covering the last 2600years. Our results prove that this corrosion clock is going on a constant pace, practically independent of the environment, making it most attractive for applications in archaeometry.

[EN] The application of solid state electrochemistry techniques for dating archaeological strata using lead-containing bronze coins is described. The proposed methodology was applied to samples coming from the Roman archaeological site of Magna Mater Temple (Rome, Italy) occurring in different strata dating back between the second half and the end of the 4(th) century A.D. and the 20(th) century. The voltammetric signatures of copper and lead corrosion products in contact with aqueous acetate buffer, as well as the catalytic effects produced on the hydrogen evolution reaction, were used for establishing the age of different strata and dating coins belonging to unknown age. Voltammetric data were consistent with a theoretical approximation based on a potential rate law for the corrosion process.

[EN] The application of solid state electrochemistry techniques for dating archaeological strata using lead-containing bronze coins is described. The proposed methodology was applied to samples coming from the Roman archaeological site of Magna Mater Temple (Rome, Italy) occurring in different strata dating back between the second half and the end of the 4(th) century A.D. and the 20(th) century. The voltammetric signatures of copper and lead corrosion products in contact with aqueous acetate buffer, as well as the catalytic effects produced on the hydrogen evolution reaction, were used for establishing the age of different strata and dating coins belonging to unknown age. Voltammetric data were consistent with a theoretical approximation based on a potential rate law for the corrosion process.

This is the peer reviewed version of the following article: Montoya, Noemí, Montagna, Elena, Lee, Yu, Domenech Carbo, Mª Teresa, Doménech Carbó, Antonio. (2017). Raman spectroscopy characterization of 10-cash productions from the late Chinese emperors to the Republic.Journal of Raman Spectroscopy, 48, 10, 1337-1345. DOI: 10.1002/jrs.5218 , which has been published in final form at http://doi.org/10.1002/jrs.5218. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving., [EN] The use of Raman spectroscopy for discriminating monetary emissions, a recurrent problem in much archaeological studies, is described. The method involves the record of Raman signatures of tenorite and crystalline and defective cuprite in the patina based on the idea that subtle, mint-characteristic variations in the composition and metallography of the base metal during the manufacturing process are reflected in the variation in depth of the composition and crystallinity of the corrosion patina. The technique was applied to a series of 10-cash copper coins produced around the transition between the Kuang Hsu and Hsuan Tung last Chinese emperors and the first Republic whose averaged composition was 95 +/- 1% wt Cu plus 5 +/- 1% wt Zn often accompanied by traces of Sn and Pb. Raman data, corroborated by focusing ion beam-field emission scanning electron microscopy and voltammetry of immobilized particles measurements, suggested the possibility of discerning between different provincial and regular unified currency productions.

This is the peer reviewed version of the following article: Doménech Carbó, A.; Domenech Carbo, MT.; Álvarez-Romero, C.; Montoya, N.; Pasies-Oviedo, T.; Buendía Ortuño, MDM. (2017). Electrochemical Characterization of Coinage Techniques the 17(th) Century: The maravedis Case. Electroanalysis. 29(9):2008-2018. doi:10.1002/elan.201700326, which has been published in final form at http://doi.org/10.1002/elan.201700326. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.", [EN] The voltammetry of immobilized particles (VIMP) methodology was applied to the discrimination of Spanish maravedis produced in 10 different mints between 1661 and 1664 using characteristic signatures for the reduction of cuprite and tenorite in the patina of the coins and catalytic effects on the hydrogen evolution reaction (HER). The variation of the apparent tenorite/cuprite ratio with depth was fitted to potential laws differing from one mint to another for A Coruna, Burgos, Cordoba, Cuenca, Granada, Madrid, Trujillo, Segovia, Sevilla and Valladolid coins. Electrochemical data permitted to detect the changes in the composition (with lowering of the silver content) and manufacturing technique (from hammer to mill) occurring in this historical period.

This is the peer reviewed version of the following article: Doménech Carbó, A.; Domenech Carbo, MT.; Álvarez-Romero, C.; Montoya, N.; Pasies-Oviedo, T.; Buendía Ortuño, MDM. (2017). Electrochemical Characterization of Coinage Techniques the 17(th) Century: The maravedis Case. Electroanalysis. 29(9):2008-2018. doi:10.1002/elan.201700326, which has been published in final form at http://doi.org/10.1002/elan.201700326. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.", [EN] The voltammetry of immobilized particles (VIMP) methodology was applied to the discrimination of Spanish maravedis produced in 10 different mints between 1661 and 1664 using characteristic signatures for the reduction of cuprite and tenorite in the patina of the coins and catalytic effects on the hydrogen evolution reaction (HER). The variation of the apparent tenorite/cuprite ratio with depth was fitted to potential laws differing from one mint to another for A Coruna, Burgos, Cordoba, Cuenca, Granada, Madrid, Trujillo, Segovia, Sevilla and Valladolid coins. Electrochemical data permitted to detect the changes in the composition (with lowering of the silver content) and manufacturing technique (from hammer to mill) occurring in this historical period.

This is the peer reviewed version of the following article: Montoya, Noemí, Montagna, Elena, Lee, Yu, Domenech Carbo, Mª Teresa, Doménech Carbó, Antonio. (2017). Raman spectroscopy characterization of 10-cash productions from the late Chinese emperors to the Republic.Journal of Raman Spectroscopy, 48, 10, 1337-1345. DOI: 10.1002/jrs.5218 , which has been published in final form at http://doi.org/10.1002/jrs.5218. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving., [EN] The use of Raman spectroscopy for discriminating monetary emissions, a recurrent problem in much archaeological studies, is described. The method involves the record of Raman signatures of tenorite and crystalline and defective cuprite in the patina based on the idea that subtle, mint-characteristic variations in the composition and metallography of the base metal during the manufacturing process are reflected in the variation in depth of the composition and crystallinity of the corrosion patina. The technique was applied to a series of 10-cash copper coins produced around the transition between the Kuang Hsu and Hsuan Tung last Chinese emperors and the first Republic whose averaged composition was 95 +/- 1% wt Cu plus 5 +/- 1% wt Zn often accompanied by traces of Sn and Pb. Raman data, corroborated by focusing ion beam-field emission scanning electron microscopy and voltammetry of immobilized particles measurements, suggested the possibility of discerning between different provincial and regular unified currency productions.

[EN] The characterization of corrosion products in leaded bronze based on the voltammetry of immobilized particles methodology is described. Voltammetric data, supported by Fourier transform infra-red spectroscopy, field emission scanning electron microscopy-energy dispersive X-ray microanalysis (FESEM-EDX) and scanning electrochemical microscopy (SECM) allow the identification of copper and lead corrosion materials. The mutual influence of such products is modeled upon considering uncompensated ohmic drops in the Tafel analysis of the rising portion of the respective voltammetric signals for their electrochemical reduction.

[EN] The characterization of corrosion products in leaded bronze based on the voltammetry of immobilized particles methodology is described. Voltammetric data, supported by Fourier transform infra-red spectroscopy, field emission scanning electron microscopy-energy dispersive X-ray microanalysis (FESEM-EDX) and scanning electrochemical microscopy (SECM) allow the identification of copper and lead corrosion materials. The mutual influence of such products is modeled upon considering uncompensated ohmic drops in the Tafel analysis of the rising portion of the respective voltammetric signals for their electrochemical reduction.

[EN] A methodology for dating copper/bronze archaeological objects aged under atmospheric environments using electrochemical impedance spectroscopy (EIS) is described. The method is based on the measurement of resistance associated to the growth of corrosion layers in EIS recorded upon immersion of the pieces in mineral water and applying a bias potential for the reduction of dissolved oxygen. Theoretical expressions for the time variation of such resistance following a potential rate law are presented. Equivalent expressions are derived and applied for estimating the variation of the tenorite/cuprite ratio from their specific voltammetric signals using voltammetry of microparticles data. Calibration curves were constructed from a set of well-documented coins.

[EN] A methodology for dating copper/bronze archaeological objects aged under atmospheric environments using electrochemical impedance spectroscopy (EIS) is described. The method is based on the measurement of resistance associated to the growth of corrosion layers in EIS recorded upon immersion of the pieces in mineral water and applying a bias potential for the reduction of dissolved oxygen. Theoretical expressions for the time variation of such resistance following a potential rate law are presented. Equivalent expressions are derived and applied for estimating the variation of the tenorite/cuprite ratio from their specific voltammetric signals using voltammetry of microparticles data. Calibration curves were constructed from a set of well-documented coins.