DOI: 10.3303/CET2398045 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Paper Received: 16 October 2022; Revised: 19 January 2023; Accepted: 6 April 2023 
Please cite this article as: Alviz-Meza A., De-Leo A., Barandiaran-Gamarra J., Torres-Salazar E., Orozco-Agamez J., 2023, Study of Silver Used 
in Peruvian Viceroyalty Objects through Chemical Analysis, Chemical Engineering Transactions, 98, 267-272  DOI:10.3303/CET2398045 
  

 CHEMICAL ENGINEERING TRANSACTIONS  
 

VOL.  98, 2023 

A publication of 

 

The Italian Association 

of Chemical Engineering 

Online at www.cetjournal.it 

Guest Editors: Sauro Pierucci, Carlo Pirola 

Copyright © 2023, AIDIC Servizi S.r.l. 

ISBN 978-88-95608-97-6; ISSN 2283-9216 

Study of Silver Used in Peruvian Viceroyalty Objects through 

Chemical Analysis 

Anibal Alviz-Mezaab*, Andrés De Leoc, José Barandiaran-Gamarraa, Edwin Torres-

Salazarb, Juan Orozco-Agamezd 

aGrupo de investigación en Deterioro de Materiales, Transición energética y Ciencia de Datos - DANT3, Faculty of 

enginering, arquitecture and urbanism, Universidad Señor de Sipán, Chiclayo, Pimentel 14001, Peru 
 bSemillero de Investigación en Corrosión de Metales, Energías Sostenibles y Análisis de Datos - COMD3S, Faculty of 

enginering, arquitecture and urbanism, Universidad Señor de Sipán, Chiclayo, Pimentel, 14001, Peru 
cResearch Center for Heritage Conservation, Universidad de Ingeniería y Tecnología - UTEC, Lima, Peru 
d Universidad Industrial Santander, Escuela de Ingeniería Metalúrgica y Ciencia de los Materiales, Grupo de 

Investigaciones en Corrosión – GIC, cra 27 calle 9, Bucaramanga –Santander, Colombia 

 alvizanibal@crece.uss.edu.pe 

The exploitation of metals such as silver and copper has been the basis of the economic and socio-cultural 

development of multiple Andean societies such as Peru. Vestiges of the main centers of colonial metallurgy are 

known for their exhibition at various points of the Andean baroque route. However, exist doubts about the 

constituent minerals that these objects may drag. A record of trace metals emitted during smelting operations 

are useful to estimate their quality and provenance. In this approach, we found viceroyalty silver objects with 

only copper as a tracer metal, in Ag/Cu ratios from 9 to 34.85. The crystalline system of both metals was found 

to be cubic in one object while other objects indicated amorphous phases for both elements. This type of 

research has the potential to be extended with other characterization techniques such as lead isotopic analysis, 

leading to the determination of the provenance of pieces today ubicated at Cusco. 

1. Introduction 

In the 16th and 18th centuries, the quality of the material used in silver objects was an extremely important issue 

for the crown of Spain and its religiosity. The precious metals had symbolic characteristics in the catholic ritual 

leading to high-quality controls in such pieces in terms of their value for the payment of taxes associated with 

the extraction and trade of silver-made artefacts from the American territory. 

A couple of studies have been dealing with chemical characterization to obtain the quality of heritage silver 

objects, focused on the viceroyalty period. One of these works was carried out in Mexico, with a chalice of a 

popular tradition called the "chalice of the twelve" because it has been referred to as the first chalice that came 

with the inaugural evangelizes that visited the new Spain territory. The SEM-EDS technique was applied to this 

chalice to ubicate its period of fabrication around the first years of the 16th century since its composition was 

rich in lead, with a lack of precious metals such as silver or gold. It was a key feature since during the first half 

of the 16th century, the use of precious metals in this type of object was not as strict as it was at the end of the 

same century (De Leo, 2021). Another example of the importance of material characterization is found in the 

work of Luisa Vetter, the only one of its kind within the Peruvian sphere, specifically, around the characterization 

of materials in colonial pieces and with biases of interest in pre-Hispanic works (Vetter, 2008). The researcher 

intended to present the possibilities that the characterization of the materials can offer by SEM-EDS, delivering 

a proposal on the percentages of the metals found; which helped to establish the legal standards that were of 

the Crown for the quality of silver pieces worked during the viceroyalty period. These findings represent the only 

research aiming to study viceroyalty objects from Peru through chemical characterization. 
In the historical history telling about silver pieces from the viceroyalty period, the silver objects made in the 

different American viceroyalty cities responded to the law of the time and to the control given to the "Caja Real", 

an institution administered by the crown that was in charge of collecting taxes. Each city with a Caja Real had 

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an "ensayador" (tester) at its service, a silversmith with outstanding reputation and skills, who verified the quality 

of the silver in objects. In general terms, before a religious or civil silver object was made, the silversmith had to 

present the silver with which the piece would be made to the tester. The metal was weighed and its quality was 

verified. After this, the silversmith returned to his workshop to make the pieces. When he finished, he returned 

to the tester with the pieces to be weighed again and quality verified. From this weight, the owner had to pay a 

fifth of the value as a tax of 20%. The tester verified that the silversmith's work did not exceed the alloy of other 

less noble metals, such as copper, and that the silver declared at the beginning was not traded illegally, evading 

taxes. In this way, each verified piece was marked with the signs of the Caja Real, the tester, the silversmith, 

and in some cases the owner. Besides, a zigzag incision that demonstrated the random extraction of metal for 

its inspection remained marked in the piece (Ruiz Medrano, 2002). Although this was the ideal of control to 

make the pieces in the territory of the American viceroyalties, the vast majority of silver objects that exist do not 

have these marks, so questions arise for the history of the art of silverware such as: Even though the production 

of silver pieces was not controlled, what alloy guidelines did silversmiths follow in the Cuzco region, Peru? 

Regarding its quality and religious use, is there a relationship between quality and use? 

2. Method and materials 

This section is divided into fieldwork, which leads to the extraction of samples, and lab work, which includes 

chemical characterization. 

2.1 Selection of objects to be studied 

Three silver pieces located in the temple San Pedro Apóstol de Andahuaylillas were selected to approach 

possible answers to the research question presented in the introduction section. This is a provincial temple 

located 35 km from the city of Cuzco, Peru. It is characterized by having a bunch of art pieces accumulated from 

the late 16th to the 19th century. Among the various silver objects in the said collection, a lectern, a chalice, and 

a ciborium were taken to be studied. Each silver object was chosen based on its era, relationship with the tester 

brands, and its use.We also collected chronological data from the three viceroyalty objects: three characteristics 

for their dating based on style and markings, and information about the use of these pieces in the catholic rituals. 

From this, the sacredness that the ciborium and the chalice must have, unlike the lectern, stands out, since 

according to the Catholic ritual, the containers of wine and wafer are sacred. It was necessary to select a surface 

that did not compromise the aesthetics of the pieces for the extraction of samples. It was determined that the 

best place for extraction was the internal parts of the objects. After selecting the areas, they were cleaned with 

cotton and isopropyl alcohol. Subsequently, a superficial section of the piece was extracted to be discarded with 

a surgical steel scalpel due to its likely contamination. Finally, with another new scalpel blade, a new extraction 

was performed in the before exposed area (previous scratch) obtaining shavings to be chemically analyzed. 

2.2 Characterization of samples 

We used Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS) and X-Ray 

Diffraction (XRD) for characterizing the extracted samples of silver. SEM-EDS supplied chemical data of the 

extracted sample while XRD indicated the crystalline phases present in the silver slivers. Table 1 shows the 

measuring parameters. 

Table 1: Characterization equipment and its operational parameters 

Technique Equipment Parameter 

SEM-EDS Quanta FEG 250, BSED-SSD, 

EDAX APOLO X 

 Voltage 25 kV, high vacuum, and detector 

resolution of 126.1 eV, Mn-𝐾𝛼 

XRD Bruker D8 Advance  

DaVinci geometry 

Voltage 45 kV, current 40 mA, scan range 

between 10 and 80 °2𝜃, step size of 0.05 

°2𝜃, and a counting time of 5 s per step 

3. Results and discussion 

This section is alienated from the methodological section, the first subsection is about the selected silver objects 

and the second is destined for the chemical analysis performed. 

3.1 Descriptions of the selected silver objects  

The chalice observed in Figure 1 is a cup used as a fundamental object for the ritual of the mass. Its function is 

to contain the wine that is transubstantiated as the blood of Christ during the ritual of the mass, according to 

Catholic belief. The Andahuaylillas’ chalice can be dated to the mid-17th century due to its shape and aesthetic 

characteristics. The absence of decoration and its smooth surfaces are characteristic of the models established 

268



at that time throughout the Hispanic territory, which denoted the importance of the form in the ritual of the mass 

(De Leo, 2022). One aspect to be highlighted of this chalice is that on the inner part of its base, it has a series 

of five incision lines, as a mark that it was quality verified by a tester. 

 

 
Figure 1: Anonymous chalice, carved silver, mid-17th century. a) tester marks. b) sample extraction point 

 

 
Figure 2: Anonymous ciborium, Carved Silver, 1575-1598. a) Caja Real, Lima. b) sample extraction point 

 

 
Figure 3: Anonymous table lectern, carved silver, 1765. a) sample extraction point. b) registration of donor and 

date 

 

The ciborium is a container that is used to store consecrated wafers (see Figure 2). The Catholic dogma 

indicates that these wafers also transubstantiate the body of Christ during the mass. This object is comparable 

to the chalice due to the simplicity of its aesthetic characteristics; however, it has a centered mark in its inner 

a) 

b) 

a) 

b) 

a) 

b) 

269



part that can be associated with the mark of the Caja Real of Lima, used between 1575 and 1598 (Esteras, 

2000). The third piece is a table lectern (see Figure 3). This object was used in the mass ritual to place the book 

of the gospels on the altar table. In this case, the piece was made of wood lined with embossed silver plates. A 

feature to highlight of this piece is that on its frontal part, it has an inscription that says “gave Dn. Mateo Baca 

in the year 1765”, with the name of the donor and the date on which the piece was made. 

3.2 Chemical characterization of samples 

The characterization of metals in artistic pieces with heritage value and the geographical tracking of the origin 

of their raw material is a topic that has had an impact on the European sphere, especially in prehistoric and 

medieval works (Hernández-Casas, 2021). In American cases, it has only been applied to pre-Hispanic works 

(Guédron et al., 2021; Macfarlane, Andrew W. Petersen, 1990), and to date, it has not been explored in 

silverware from the viceroyalty period, covering the entire Spanish-American territory. 

Figure 4: Backscattered electrons images obtained of the internal part of a) lectern, b) chalice, and c) ciborium 

silver objects 

The use of chemical analysis to explore the composition of metal artefacts has been triggered by the appearance 

of cutting-edge technologies such as X-ray fluorescence, atomic emission spectrometry, and isotopic analysis. 

This technological revolution of the 20th century has shed light on the origin of heritage objects made from 

copper, silver, or their alloys (Pernicka, 2013). The methods employed to reveal the provenance of metals 

suggest the combination of two techniques: one based on the elemental composition analysis of the objects and 

another based on their isotopic analysis of minerals, including those of mercury (Cooke et al., 2013). In Peru, 

some studies have limited the use of XRF and pXRF (portable) to determine the origin of minerals (Craig et al., 

2007). Meanwhile, in Lake Titicaca (Guédron et al., 2021), Hualgáyoc (Macfarlane, Andrew W. Petersen, 1990), 

and in Castillo de Huarmey (Kałaska et al., 2022) isotopic analysis has been used, since elemental analysis 

may be insufficient for the precise determination of the silvers’ mine origin (Gale and Stos-Gale, 2000). The 

a)                                                                    b) 

c) 

270



study of trace elements present in artefacts made of silver is useful in cases described previously for copper 

alloys (Pernicka 2013) when the trace metals of the objects can be associated with particular quarries. In those 

cases, XRF and SEM-EDX measurements are focused on the ratios of silver to the rest of the elements present, 

to aim to explore the provenance, based on comparisons with various heritage objects (classification) and mine 

soils with exclusive trace elements (Isa-adaniya et al., 2022). For example, trace traces of silver, antimony, and 

nickel have worked to study the provenance of copper (Merkel, 1990). Our results of SEM-EDS showed that 

copper is the only metal presented in the studied silver objects (see Figure 4), covering a range between 9 and 

34.85 in the Ag/Cu ratio, as observed in Table 2. Probably, the chalice was intentionally made highly rich in 

silver due to its spiritual meaning in the catholic context. Besides, it should be noted that we found a mark or 

certification of high-quality silver in the chalice at the moment of extracting the samples. Although the precision 

of the measurements is relevant, it has been reported that the minerals present in the quarries cover 

representative ranges of an order of magnitude, so the elemental patterns -fingerprint- have turned out to be 

more decisive (Radivojević et al., 2010). Then, as determined in the well-known Stuttgart project -copper 

provenance-, chemical analyses by themselves fail to determine the provenance of metals due to: chemical 

heterogeneities in mineral deposits, variable fractionation of chemical elements between ores, slag, and 

primitive smelting processes (Stos-Gale and Gale, 2009). 

On the other hand, XDR results (see Figure 5 and Table 3) aimed to add information about the crystalline phases 

that may be present in viceroyalty silver objects. This statement does not represent all the characterized objects 

since the lectern and the chalice did not provide data about crystalline systems. Finally, all the collected chemical 

evidence is released to be used as a complement to isotopic analysis in a future study. 

Table 2: %wt. results of the SEM-EDS analysis taken to the samples shown in Figure 1 

 C O Cu Ag Ag/Cu ratio 

Lectern  Balance 5.65 8.28 79.93 9.65 

Chalice  Balance 5.17 2.44 85.03 34.85 

Ciborium Balance 7.10 9.29 83.61 9.00 

Figure 5: XRD pattern obtained from the Ciborium sample 

Table 3: Peak details of the XRD pattern of Figure 2 

Reference 

code 

Crystal system Pos. [°2θ] Height [cts] FWHM  

Left [°2θ] 

d-spacing [Å] Rel. Int. [%] 

00-004-0783 Ag - Cubic 44.4518 120.69 0.3936 2.03812 100.00 

00-004-0836 Cu - Cubic 43.0814 85.57 0.4920 2.09972 70.90 

00-004-0836 Cu - Cubic 73.7952 43.45 0.7872 1.28407 36.01 

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4. Conclusions 

This research aims to provide chemical data through SEM-EDS and XRD techniques of selected silver 

viceroyalty objects from Cusco, Peru. As a result, copper was found as the only trace metal in the heritage 

objects, covering an Ag/Cu ratio range from 9 to 34.85. Moreover, both copper and silver presented a cubic 

crystalline system in one sample while both were amorphous in another sample. These results may be used as 

income data for a study focused on determining the provenance of these objects using isotopic analysis. 

Acknowledgments 

The authors express their gratitude to the Universidad Señor de Sipán for funding the research project under 

code 133-2022/PD-USS. Equally, the authors are grateful to the Universidad Complutense de Madrid for 

providing access to their characterization laboratories, especially to professor Francisco Javier Pérez Trujillo. 

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	Study of Silver Used in Peruvian Viceroyalty Objects through Chemical Analysis