ORIGINAL RESEARCH

published: 29 July 2020

doi: 10.3389/fmats.2020.00230

Microchemical Investigation of
Long-Term Buried Gilded and
Silvered Artifacts From Ancient Peru
Gabriel M. Ingo 1* , Monica Albini 1 , Angel D. Bustamante 2 ,
Sandra del Pilar Zambrano Alva 2 , Arabel Fernandez 3 , Chiara Giuliani 1 , Elena Messina 1 ,
Marianna Pascucci 1 , Cristina Riccucci 1 , Paola Staccioli 1 , Gabriella Di Carlo 1 and
Luca Tortora 4
1
Institute for the Study of Nanostructured Materials, National Research Council, Rome, Italy, 2 Departamento Académico
de Física del Estado Sólido, Universidad Nacional Mayor de San Marcos, Lima, Peru, 3 Museo Señora de Cao
and Fundacion Wiese, Trujillo, Peru, 4 Surface Analysis Laboratory, Istituto Nazionale di Fisica Nucleare (INFN) & Department
of Mathematics and Physics, Roma Tre University, Rome, Italy

A large number of metal artifacts with exceptional artistic value of the Moche culture
have been found in the tombs of the Lords of Sipán (Lambayeque, Peru) and of the
Edited by: Lady of Cao (El Brujo, Peru) characterized by different burial conditions. Some of the
Tadeusz Hryniewicz,
Koszalin University of Technology,
objects, dated around 300–400 AD, are constituted by substrates of Cu- or Ag-based
Poland alloys coated by uniformly distributed thin films of precious metal (1–4 microns) that
Reviewed by: create also polymetallic bicolored surfaces with “gold” and “silver” areas. In order to
Jude Mary Runge,
investigate the corrosion product structure and composition as well as to identify the
CompCote International, Inc.,
United States techniques used to give the gold or silver appearance, an integrated analytical approach
Emma Paola Angelini, has been adopted. The selected complementary methodologies were scanning electron
Politecnico di Torino, Italy
microscopy (SEM) coupled with energy-dispersive spectroscopy (EDS), X-ray diffraction
*Correspondence:
Gabriel M. Ingo
(XRD), X-ray photoelectron spectroscopy (XPS), and optical microscopy (OM). The
[email protected] findings reveal that the substrates are mainly composed of Cu-Ag-Au alloys that at the
site of Sipán have been almost completely corroded during the burial. Furthermore, the
Specialty section:
This article was submitted to results show that the main aggressive agent is Cl− coming from the soil and that
Environmental Materials, the degradation phenomena were likely enhanced by the galvanic coupling between
a section of the journal
the precious metal layer and the less noble substrate. The degradation products
Frontiers in Materials
have formed mainly layered structures containing chloroargyrite (AgCl), cuprite (Cu2 O),
Received: 29 November 2019
Accepted: 23 June 2020 nantokite (CuCl), and atacamite [CuCl2 .3Cu(OH)2 ] polymorphs. These latter species
Published: 29 July 2020 warn that dangerous copper cyclic corrosion is occurring, a harmful phenomenon,
Citation: commonly defined as “bronze disease,” which must be firmly mitigated. Finally, the
Ingo GM, Albini M,
Bustamante AD, Zambrano Alva SdP, findings reveal that the Moche metal workers used the depletion gilding to selectively
Fernandez A, Giuliani C, Messina E, modify the surface chemical composition of the artifacts to produce the Ag or Au thin
Pascucci M, Riccucci C, Staccioli P,
films. According to this subtractive method, the surface of the Cu-Au-Ag alloys was
Di Carlo G and Tortora L (2020)
Microchemical Investigation enriched with a layer of precious metal by means of cycles of thermal treatments and
of Long-Term Buried Gilded removal of Cu or both Cu and Ag from the outermost region by using pickling solutions.
and Silvered Artifacts From Ancient
Peru. Front. Mater. 7:230. Keywords: Cu-Ag-Au ternary alloys, long-term burial soil corrosion, surface analytical techniques, metal surface
doi: 10.3389/fmats.2020.00230 chemical modification, galvanic coupling, tumbaga

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Ingo et al. Microchemistry of Corroded Gilded Artifacts

INTRODUCTION broken during the cleaning and conservation procedures. For

XRD measurements, low quantities of patina have been also
In 1987, great treasures composed of spectacular metal artifacts carefully removed from the objects and properly ground. The
were discovered in the unlooted tombs of the Lords of Sipán samples were subjected to metallographic, microchemical, and
(Huaca Rajada, Lambayeque, Peru), and in 2006, in the tomb structural investigations in as-received conditions by means of
of the Lady of Cao (El Brujo, Trujillo, Peru). These sites are the abovementioned analytical techniques. Furthermore, some
characterized by different burial conditions that have influenced fragments also have been cross-sectioned to study the structure
the long-term corrosion behavior. Indeed, the artifacts found at of the corrosion products and of the thin Ag or Au surface layers.
Sipán are extensively corroded, while the objects found at El Brujo In order to prepare the cross sections, representative shards have
are generally in a good state of preservation. The extraordinary been embedded in a suitable two-component resin (curing time:
artifacts found there, mainly jewels and ceremonial ornaments, 1 day) and sectioned by using a diamond saw able to retain the
were produced by the metal smiths of the Moche culture that outermost layer’s features and the bulk microchemical structure
flourished on the northern coast of present-day Peru between (Ingo et al., 2013a). The polishing procedure was performed
about 0 and 600 AD. The discovery of these amazing artifacts by using silicon carbide papers until 1,200 grit, while the final
confirms that the Moche metal workers were sophisticated pre- treatment was carried out with diamond pastes up to 0.1 µm.
Columbian producers of unequaled metal objects. Some of them
show a bicolored aspect since characterized by a polymetallic Scanning Electron Microscopy –
surface with thin “gold” and “silver” areas likely achieved by using Energy-Dispersive Spectroscopy
manufacturing methods able to precisely manipulate the surface
chemical composition at a nanoscale dimension.
Analysis
In order to investigate the microchemical surface and bulk The surface morphology and microchemical structure have
structure and the degradation products formed during the long- been investigated by means of a thermionic scanning
term burial, we have adopted an integrated analytical approach electron microscope (SEM) Stereoscan 360 (Cambridge,
by using complementary methodologies such as scanning United Kingdom) and a high-spatial resolution LEO 1530 field
electron microscopy (SEM) combined with energy-dispersive emission scanning electron microscope (FE-SEM). SEM and
spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), FESEM instruments are equipped with an INCA 250 and INCA
X-ray diffraction (XRD), and optical microscopy (OM). 450 energy-dispersive spectrometer (EDS), respectively, and
It is worth noting that the interaction between these back-scattered electron (BSE) detectors. SEM investigations were
polymetallic (Ag-Cu-Au) artifacts and the soil constituents has performed by using both secondary (SE) and BSE electrons and
lasted many hundred years, and the information on the resulting selecting an acceleration voltage of 20 kV, while the FE-SEM
products could be of great interest in the study of long-term characterizations were carried out by varying the acceleration
environmentally driven degradation phenomena of polymetallic voltages from 1 to 20 kV in order to better disclose the
materials, phenomena that until now have been investigated micromorphological features.
by few authors (Scott, 1986, 1998; Hörz and Kallfass, 2000; In order to investigate the powered materials, a suitable
Ingo et al., 2013a,b). double-faced adhesive carbon tape was used to collect and fix the
Our effort was also aimed to gain further insights into matter. These carbon tapes are commonly and conveniently used
methods used by the Moche metallurgists to modify the surface for SEM-EDS microchemical investigations (Ingo et al., 2001).
chemical composition (Lechtman, 1971, 1979; Lechtman et al., In order to avoid charging effects induced on the sample by the
1982; Lechtman, 1984a,b; Scott, 1986, 1998, 2000; Hörz and electron beam, the surfaces of the samples were coated with a
Kallfass, 1998, 2000). We point out that the selected artifacts thin layer of Cr or C, deposited by using a Bal-Tech SCD 500
were not objects of common use but ornaments for an elite equipment at a pressure of about 5 × 10−3 mbar to achieve a
exhibiting power and rank. They include high-status ceremonial conductive and uniform film, a few nanometers thick.
objects and spectacular nose ornaments, i.e., the narigueras,
large jewels to be hooked to the nostrils. These artifacts clearly X-Ray Diffraction Investigation
demonstrate the outstanding virtuosity of the Moche artisans XRD investigations were carried out by analyzing directly the
and the impressive quality of their metal production as well as artifact surfaces or the small amount of powdered patina by using
reflect the most sophisticated metal production techniques of that a Siemens 5000 X-ray powder diffractometer with Ni-filtered Cu
period in the New World. Kα radiation (λ = 0.154056 nm). The following experimental
parameters were selected: angular values between 10 and 90◦ in
additive mode, step size 0.05◦ , and sampling time of 20 s. XRD
EXPERIMENTAL DETAILS patterns were analyzed by using specific electronic databases and
compared with the literature information.
Archeological Artifacts
The archeological artifacts to be analyzed have been selected by Optical Microscopy Study
the archeologists. The samples are mainly fragments detached OM morphological studies were performed by using a Leica
from the artifacts likely being crushed by pressure from the soil MZFLIII and a Leica Application Suite (LAS) multifocus stereo
sediments during the long-term burial or small parts accidentally microscope. Furthermore, at the Museum of the Lady of Cao, a

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Ingo et al. Microchemistry of Corroded Gilded Artifacts

Zeiss optical microscope equipped with a digital camera was used or randomly scattered particles of reddish cuprite (Cu2 O) and
for in situ morphological investigation. The metallurgical features yellow-orange nantokite (CuCl) inside the patina.
of the cross-sectioned artifacts have been studied by means of a Since the presence of atacamite corrosion products in bronze
Leica MEF IV optical microscope. archeological objects is a symptom of the detrimental “bronze
disease” degradation phenomenon, great attention must be paid
X-Ray Photoelectron Spectroscopy to avoid its insurgence and development. This relentless and
The XPS technique has been used to ascertain the surface possible cyclic corrosion process is caused by the presence of chlorine in
presence of alloying elements such as As or Sn (Lechtman the burial environment that corrodes copper forming nantokite
and Klein, 1999). Measurements were carried out by using an (Scott, 1990, 1991, 2002; Bastidas et al., 2010). When this latter
ESCALAB Mk II spectrometer equipped with a hemispherical specie is exposed to moisture and oxygen, it gives rise to the
electron energy analyzer and a twin anode X-ray source emitting formation of atacamite or its polymorphs [2Cu2 (OH)3 Cl] and
not monochromatized Al Kα and Mg Kα radiations, 1,486.6 hydrochloric acid which in turn reacts with copper to form new
and 1,253.6 eV, respectively. The binding energy (BE) accuracy nantokite in a cyclic and self-sustaining process that converts
has been measured to be ± 0.1 eV. The values of the BEs of copper in atacamite.
the Au 4f7/2 signal from Ar+ -cleaned Au 99.99%, of the Zr As a consequence of this phenomenon, the surface of the
3d5/2 peak from zirconia, and of Sn 3d5/2 peak from cassiterite object is transformed into a light greenish powder, thus inducing
(SnO2 ) were 84.0, 182.3, and 487.0 eV, respectively (Paparazzo the progressive loss of its original form and integrity (Ingo et al.,
et al., 1988; Ingo et al., 1992; Ingo and Padeletti, 1994; Curulli 2013b). At present, different conservation materials and methods
et al., 2005). In order to avoid, or reduce, any eventual sample are used to hinder the degradation process. Unfortunately, some
damage potentially provoked by the x-ray irradiation during the of these procedures are based on the use of toxic inhibitors
XPS measurements, short acquiring times were imposed and a (Stupnišek-Lisac et al., 1998; Antonijevic and Petrovic, 2008) but
copper sample holder cooled by liquid N2 was used (Schlesinger tailored innovative solutions based on nanostructured materials
et al., 2000). Other experimental details are reported elsewhere are emerging for bronze conservation and cleaning similar to
(Ingo et al., 2000, 2002). those used to stop degradation of other classes of ancient works of
art (Chelazzi et al., 2014; Baglioni et al., 2015; Poggi et al., 2016).
In order to monitor the presence of Pb, Sn, or As also as
RESULTS AND DISCUSSION surface enrichment (Lechtman and Klein, 1999) from the Cu-Ag-
Au substrate caused by corrosion phenomena, we have used the
The paper presents some highlighting cases of study describing XPS technique (Ingo et al., 2002, 2013b; Hayez et al., 2004). The
the microchemical features of long-term buried Cu-Ag-Au results (not shown) reveal that neither Pb nor As is present in
alloy artifacts whose outermost chemical composition was the metallic state or as oxides and further exclude the presence in
intentionally modified to achieve a local accentuated Ag or Au the corrosion products of cassiterite (SnO2 ) or romarkite (SnO)
surface amount. This latter in some cases formed polymetallic (Paparazzo et al., 1988; Ingo et al., 1992), thus suggesting the
bicolored surfaces with “gold” and “silver” areas likely for absence of As, Pb, and Sn in the Cu-Ag-Au alloy.
symbolic, shamanic, or religious reasons. Other information is given by the SEM images and EDS
The aim of the ancient goldsmiths was to give to the spectra of the cross-sectioned fragment shown in Figure 1 that
objects the appearance of solid precious metal or to describe the microchemical structure of the artifact (˜0.2 mm
create an elaborate and fascinating specific visual effect thick). The object is almost completely mineralized, and the
combining the color of different metals (Oddy, 1981, 1990; only survived pristine metal is the thin gold layer originally
Raub, 1986a,b; Schorsch, 1988; Bray, 1993; Merkel et al., on the surface and now almost entirely embedded in the Cu
1995; Hörz and Kallfass, 1998, 2000; Grimwade, 1999; corrosion products.
Centeno and Schorsch, 2000; Ingo et al., 2013a). The gold layer (2–3 µm thick; Figure 1 and Supplementary
The first case describes the surface and bulk microchemical Figure S1) contains a low amount of silver and copper
and morphological features of a gilded semicircular diadem, an and is uniformly distributed over the entire surface on both
owl crown, almost completely mineralized) found in the tomb sides of the hammered sheet substrate marking the original
T15 at Sipán (Peru) where a young warrior was interred. surface of the object.
The OM images and the XRD pattern reported in Figure 1 The presence of Au and Ag is well documented also in the
show areas of the bare original gilded surface embedded in light inner part of the object as shown by the BSE SEM images and the
green-blue corrosion products, i.e., the patina. This structure EDS spectra of the light gray areas scattered everywhere inside the
suggests to the conservators to pay a great deal of attention during mineralized substrate. These local enrichments of precious metals
the cleaning procedure to avoid the loss of the thin gold layer that indicate the use of a “tumbaga” Cu-based ternary alloy containing
could be peeled away (Scott, 1990, 1991, 2002; Ingo et al., 2013b). an appreciable content of gold and a small amount of silver.
The results reveal that the corrosion products are mainly As a consequence of the long-term interaction with the
constituted by atacamite and its polymorph paratacamite [basic surrounding environment, silver has reacted with chlorine from
copper oxy-chloride, Cu2 Cl(OH)3 ], thus demonstrating that the the soil and it has been transformed in chlorargyrite (AgCl),
main aggressive agent coming from the burial environment is while gold has formed small metallic nanoparticles distributed in
chlorine. Furthermore, the findings show the presence of a layer the mineralized substrate. Furthermore, EDS spectra confirm the

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Ingo et al. Microchemistry of Corroded Gilded Artifacts

FIGURE 1 | SEM, EDS (spectrum A–E), OM and XRD results describing the micro-chemical of a fragment of a gilded semicircular diadem (tomb T15 of a young
warrior, Sipán). OM images and XRD pattern show the green patina composed of acicular atacamite [Cu2 Cl(OH)3 ] with areas of the bare original gilded surface. The
OM image discloses also layered particles of reddish cuprite (Cu2 O) and yellow-orange nantokite (CuCl).

absence of Pb, As, and Sn in the substrate as already documented alloy substrate. However, the gold content may be estimated to
by XPS for the external surface (Lechtman and Klein, 1999). be around 10–15 weight percent (hereafter wt%).
The severe corrosion process occurring during the It is worth noting that the corrosion of copper is
long-term burial does not allow determining precisely the likely enhanced by the presence of the precious metal
chemical composition of the tumbaga Ag-Cu-Au ternary alloy layer since a relevant degradation driving force could
(Twilley and Boyles, 1981). Therefore, it cannot be possible to be the difference between the electrochemical potentials
determine the relative proportions of metals which constitute the of Cu and Au or Ag along with the soil characteristics

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Ingo et al. Microchemistry of Corroded Gilded Artifacts

(pH, humidity, presence of aggressive ions) that could realized that an alloy surface could be modified by empirically
increase the transformation of Cu and Ag into minerals optimized treatments and that unique symbolic and esthetic
(Ingo et al., 2013a,b). features could be achieved.
The severe alteration phenomena could have been probably It is worth pointing out that the aim of the Moche
exacerbated by the galvanic corrosion, also known as dissimilar metallurgists was not fraudulent as frequently observed in the
metal corrosion or bimetallic corrosion. This latter destructive Old World (Lins and Oddy, 1975; Lechtman, 1979, 1984a,b;
reaction is an electrochemical process occurring when two or Scott, 1986, 1998, 2000; Schorsch, 1988; Oddy, 1991; La Niece,
more metals are in contact in the presence of an electrolyte and a 1993; Zwicker et al., 1993; Cooke et al., 2008; Ingo et al.,
corrosive environment. 2013b). Their aim was only finalized to modify color and
Under these conditions, the less noble metal acts as an esthetic appearance of an object combining different metals as
anode and is preferentially corroded at an accelerated rate if Cu, Au, and Ag on the artifact surface, thus stimulating the
compared with the uncoupled condition (Ingo et al., 2013a,b). development of sophisticated methods acting on a nanoscale as
On the contrary, the other more noble metal acts as a cathode the electrochemical replacement plating discovered by Lechtman
and remains protected until the less noble metal is completely (1971, 1979, 1984a,b) and Lechtman et al. (1982). Other
transformed in corrosion products. As mentioned above, the techniques were also developed to alter the surface chemical
extent of corrosion depends on the difference between the composition such as the foil gilding or the fusion gilding
electrochemical potentials of the involved metals and makes the use of which can be determined only by examining
gilded-metal artworks particularly unstable from a chemico- the ancient gilt surfaces via microchemical investigations
physical and structural point of view. (Scott, 1986, 1998, 2000; Cooke et al., 2008).
Our findings suggest that the electrochemical oxidation– The second case study is a gilded plaque, completely
reduction process could have enhanced the degradation of these mineralized, found in the tomb T16 of a warrior found with
polymetallic objects having created a galvanic cell formed by a “Pututo,” i.e., a ceremonial trumpet produced by using
the precious metal layer connected to the substrate with water a great seashell.
and dissolved ions that provide a means for ion and electron The high-spatial resolution SEM images shown in Figure 2
migration (Ingo et al., 2013a,b). (first row) describe the morphology of the surface gold-enriched
Concerning the manufacturing techniques used by the Moche layer present on both sides, while the other SEM and EDS results
metallurgists, the above shown results exclude the application of allow to evaluate the internal corroded structure of the artifact.
a thin gold film via mechanical or metallurgical methods and The high-spatial resolution SEM images (first row) reveal the
suggest the use of the gilding process to remove copper from a presence of not uniformly distributed micro and nano pitlike
tumbaga substrate to create an Au-looking surface. According to pores on the surface of the gilding layer. The development of
this bottom-up subtractive method, an artifact appearance could this morphological feature could be related to the procedures
be substantially modified, rendering the objects golden or silvery adopted for the formation and removal of oxides such as
even if the amount of Au or Ag in the alloy was relatively low. temperature and duration of thermal treatments as well as to the
As described by other scholars, the depletion gilding is based pickling conditions.
first on the surface oxidation of Cu from the near-surface region The thickness of the gilding layer is not uniform and ranges
that is favored as compared to Au or Ag (Lechtman, 1971, 1979; from about 2–4 µm and is mainly composed of Au with a
Forty, 1979; Forty and Durkin, 1980; Lechtman et al., 1982; consistent presence of Ag and Cu. Also for this object the Moche
Lechtman, 1984a,b; Scott, 1986, 1998, 2000; Hörz and Kallfass, metalworkers used a tumbaga Cu-based alloy with gold and some
1998, 2000; Sáenz-Samper and Martinón-Torres, 2017). silver as documented by the BSE SEM images and the EDS spectra
The removal of Cu oxides was carried out by immersing the of the cross-sectioned fragment. These results also reveal the
oxidized artifact in a poultice of an acid plant juice containing presence of consistent amounts of Ag and Au in the light gray
likely other appropriate corrosive chemical compounds that areas of the completely mineralized substrate and of chlorine as
progressively dissolved copper oxides from the surface and main degrading agent.
created a fine outermost layer of precious metal. In this way, Another interesting object found at Sipán is a silver-
an Ag or Au spongy crust on the surface was formed and then plated nariguera found in the tomb T16 of the warrior with
burnished, leaving a brilliant finish. a Pututo. The SEM-EDS results shown in Figure 3 reveal
The success of the process depends mainly on the skill of that the artifact is constituted by an Ag-based alloy whose
the artisans that empirically selected not only the alloy chemical surface was deliberately enriched in silver. The SEM and OM
composition but also the pickling solutions (Forty, 1979; Forty images and EDS spectra show that it is almost completely
and Durkin, 1980; Lechtman et al., 1982; Hultquist, 1985; mineralized and describe the microchemical structure of the
Guisbiers et al., 2014). surface silver-enriched layer as well as show the internal corroded
The artifacts found at Sipán and Trujillo demonstrate that structure of the artifact. The XRD pattern of the green copper
the Moche artisans were able to effectively control the selective corrosion product (third row, Figure 3) also in this artifact
removal of copper oxides (and sometimes silver) from the reveals the presence of harmful atacamite that is present also
surface, creating a homogeneous distribution of Au or Ag along inside the artifact (see the OM image shown in the third
the surface (Ingo et al., 2013a,b). This ability was based only on row of Figure 3), thus confirming the role of chlorine in the
the long-term cognitive skill of the Moche metal workers who corrosion process.

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FIGURE 2 | SEM images and the EDS spectra (A–F) of a fragment of a gilded plaque completely mineralized found in the tomb T16 of the warrior with a ceremonial
trumpet called Pututo. The results describe the microchemistry and the morphology of the surface gold-enriched layer present on both sides as well as show the
internal corroded structure of the artifact.

Unfortunately, the conditions of the investigated artifacts features of the Ag-Cu-Au alloys used by the Moche metallurgists;
found at Sipán do not allow the determination of detailed therefore, our investigations have been focused also on the
information on the chemical composition and metallurgical well-preserved artifacts found in the tomb of the lady of Cao

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FIGURE 3 | SEM and OM images and EDS spectra (A–D) of a fragment of a silver plated nariguera almost completely mineralized found in the tomb T16 of the
warrior with a ceremonial trumpet called Pututo. The results describe the micro-chemical structure of the surface silver-enriched layer as well as show the internal
corroded structure of the artifact. The XRD pattern of the green copper corrosion product (third row) reveals the presence of harmful atacamite that is present also
inside the artefact (see the OM image shown in the third row).

whose environment was different with respect to that of Sipán Some morphological details are shown by the optical images
being desert-arid. reported in Figures 4, 5 that disclose the smooth interface
In particular, we have investigated some narigueras, i.e., large between the “gold” and the “silver” areas characterized by a color
jewels to be hooked to the nostrils, that have been found with the change variation quite sharp without a morphological variation.
mummy of the Lady of Cao; she was also well-preserved by the We have had the possibility to investigate in detail
arid burial condition. a small fragment detached from the “silver” area of the
The narigueras are generally in a very good state of head of the animal on the left of the narigeura F4-03
conservation and are generally characterized by well-evident (Figure 5). The FE-SEM images and the EDS spectra of
“silver” and “gold” surfaces as depicted in Figures 4, 5 the cross-sectioned fragment shown in Figures 5, 6 and
where the front and back of the nariguera F4-22, F4-24, and Supplementary Figure S2 reveal the metallurgical features of
F4-03 are shown. the single sheet constituting the nariguera while in Table 1

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FIGURE 4 | The front and back of the nariguera F4-22 from the tomb of the Lady of Cao and optical images of the interface between the gold- and the
silver-enriched areas, on the first and second rows, respectively. In the third row is shown the front and back of the nariguera F4-24. The images of the narigueras
clearly reveal the color change from the “silver” and “gold” surface.

are reported the EDS elemental semiquantitative compositions This structure is similar to that observed in the nariguera
expressed as weight percent (wt%). These latter data reveal the found at Sipán in the tomb 16 and shown by the SEM and OM
use of a deliberate ternary alloy of Ag, Cu, and Au to produce the images reported in Figure 3; therefore, from the comparisons
narigeura F4-003. between these structures, we can evaluate the effect of the
The BSE SEM and the EDS results of the cross-sectional view long-term corrosion phenomena that occurred in the soil to the
through the nariguera show a lamellar-fibrous structure with an buried Ag-Cu-Au artifacts.
array of periodical alternating light and gray semi-aligned layers As evidenced by the EDS results reported in Figure 6 and
quite parallel to the surface. Tables 1, 2, the alternated layers of the bulk structure are

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Ingo et al. Microchemistry of Corroded Gilded Artifacts

FIGURE 5 | The nariguera F4-03 from the tomb of the Lady of Cao and an optical image the interface between the “gold” and the “silver” areas, on the left and right
side of the first raw, respectively. SEM images and EDS spectra (M1, M2, A–F) of the different areas of a cross-sectioned fragment of the nose ornament taken in the
silvered area of the head of the animal on the left, second and third raw, respectively. The EDS elemental semi-quantitative composition (expressed as wt%) are
reported in Table 1.

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Ingo et al. Microchemistry of Corroded Gilded Artifacts

FIGURE 6 | SEM image and EDS spectra (A–D) of the different areas of the alloy matrix of the nose ornament (nariguera) F4-03 from the tomb of the Lady of Cao.
The EDS elemental semi-quantitative chemical composition (expressed as wt%) are reported in Table 2.

TABLE 1 | Energy-dispersive spectroscopy (EDS) elemental composition [expressed as weight percent (wt%)] of the different areas of the cross-sectioned fragment of
the nariguera F4-03 from the tomb of the Lady of Cao.

Spectrum O Si S Cl Cu Ag Au

M1-alloy matrix* – – – – 18.18 70.41 11.40

M2-alloy matrix* – – – – 17.96 70.08 11.96
A-white thin layer – – – – 6.07 77.06 16.88
B-gray areas under the white thin layer 10.20 – – 6.15 31.66 32.75 19.24
C-small white particles 10.70 3.88 0.25 – 2.30 82.87 –
D-white thin layer 1.73 3.43 – 2.10 68.83 23.91
E-gray areas under the white thin layer 7.41 0.44 – 2.37 20.56 49.19 20.03
F-small white particles 3.75 0.98 11.64 1.36 – 83.63 –

The EDS spectra are shown in Figure 4. *Analyzed area 100 µm × 100 µm.

characterized by different amounts of Au, Cu, and Ag being the originated by the drastic deformation of a heterogeneous
bright areas Ag-enriched, while the gray ones are Cu-enriched. material where segregation areas have been formed.
The data reported in Tables 1, 2 are in agreement with This phenomenon presumably occurred during the
the information achieved by Cesareo et al. (2016, 2017) solidification of the cast Ag-based alloy (Hörz and Kallfass,
and Cesareo (2019), private communication during an in situ 1998, 2000) and has given rise to the formation of
investigation carried out at the Museum of the Lady of Cao Cu-enriched areas in the melt containing more precious
by using a portable X-ray fluorescence (XRF) apparatus. The metals and less Cu.
reliability and utility of this analytical approach have been SEM images clearly show that the material was subjected
already largely demonstrated in the study of cultural heritage to heavy deformation by mechanical working carried out to
artifacts being a rapid and useful method to evaluate the reduce the thickness of the sheet and by the embossing and
elemental surface content of metals and degraded surfaces punching during the manufacture of the nariguera. The intense
(Angelini et al., 2006; Figueiredo et al., 2010; Galli et al., 2011; hammering process have elongated the Cu-enriched areas to
Trojek and Hlozek, 2012). form thin parallel layers whose shape was slightly modified by
SEM images shown in Figures 5, 6 also reveal the thermal treatment of annealing carried out to restore ductility
that the metallurgical structure reasonably has been before the final depletion gilding process.

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TABLE 2 | Energy-dispersive spectroscopy (EDS) elemental composition of the appearance up to change their aspect where this desired specific
different areas present in the alloy matrix of the nariguera F4-03 from the tomb of
effect was required.
the Lady of Cao.
This advanced skill was employed to produce elaborate
Spectrum Cu Ag Au artifacts with polymetallic surfaces and complex shapes of
spectacular beauty with symbolic, shamanic, or religious
A-white areas 11.98 76.07 11.95
values to be worn by an elite of the highest status,
B-white areas 6.71 83.27 10.02
exhibiting power and rank.
C-gray elongated phases 40.61 45.50 13.89
D-gray elongated phases 20.79 67.54 11.67

The EDS spectra are shown in Figure 5. It is worth noting that the presence of
Cu in the Ag-based alloy gives some practical advantages to the nose ornament
CONCLUSION
because it increases the mechanical features of the alloy with respect to the pure
silver. This study highlights the analytical ability of micro-destructive
surface and bulk techniques in providing a detailed information
on the long-term interaction between polymetallic artifacts and
After repeated cycles of hammering and annealing treatments surrounding environment that has caused at the Sipán site the
of a single Ag-based alloy sheet, the depletion gilding finally almost complete mineralization of the objects.
removed Cu or Cu and Ag from the near-surface region forming The integrated analytical approach based on the use of
an outermost silver- or gold-enriched layer, respectively. The complementary techniques such as SEM-EDS, XPS, OM, and
formation of a “gold” or a “silver” surface was achieved likely by XRD allows to describe the naturally grown degradation products
tuning the pickling procedures and agents. resulting from interactions between soil species and Ag-Cu-Au
The presence of these inhomogeneous structures has clearly ternary alloys and disclose that the main aggressive agent is Cl−
influenced the environmentally driven alteration phenomena, from the burial soil.
thus giving rise to the formation of peculiar corrosion The microchemical information suggests also that the
products and structures. degradation phenomena were probably enhanced by the galvanic
Our results provide some other interesting information on coupling between the precious metal layer and the less
the pickling procedures. The images shown in Figure 4 reveal noble substrate.
that the narigueras have been dipped up to half its height in a The corrosion process formed mainly layered structures
solution or wrapped in a poultice that removed, in a targeted containing chloroargyrite (AgCl), cuprite (Cu2 O), nantokite
manner, copper and silver from different areas of the object to (CuCl), and atacamite [CuCl2 ·3Cu(OH)2 ] polymorphs. This
achieve a seemingly bicolored metallic surface characterized by a information is useful to select tailored conservation materials
spectacular dual esthetic effect. and procedures for a long-term reliable conservation since the
As shown by the OM images of the front and the back of the presence of atacamite warns that the dangerous copper cyclic
nariguera F4-24 (Figure 4 and Supplementary Figure S3), the corrosion is occurring and must be firmly mitigated to transmit
color change from the “silver” and “gold” surface is quite sharp these fascinating artifacts to future generations.
and the interface smooth without any morphological variation. Finally, the combined use of different investigation
The reasons of combining gold and silver surfaces in these methodologies has given information useful to identify the
nose ornaments, sometimes rarely also with copper, with a manufacturing methods used by the Moche goldsmiths to
typical duality, could be presumably ascribed to a symbolic chemically modify the surface of Cu-Au-Ag alloys in some
and spiritual meaning, perhaps to be related to an astral or case achieving the contemporaneous presence of “gold” and
religious rationale. Some scholars believe that Au was considered “silver” areas. The depletion gilding was the method used by
to be the rain or the sweat of the sun and Ag the rain the Moche metallurgists to create these amazing esthetic effects
or the tears of the moon (Lechtman et al., 1982; Jones and by manipulating the surface of Cu-Au-Ag ternary alloys at a
Heidi, 2002; Cooke et al., 2008) or that gold could be related nanoscale dimension for creating adherent precious metal layers
to the masculinity and the right side of the humans while with a thickness ranging from one to a few micrometers.
silver could be associated to the femininity and the left side
(Hörz and Kallfass, 1998, 2000). However, it seems that gold
and silver were associated in some way to the sun and the DATA AVAILABILITY STATEMENT
moon, respectively, with a religious symbolism likely related to
the nature duality. All datasets generated for this study are included in the
However, the production of bicolored polymetallic surfaces article/Supplementary Material.
was made possible by the local availability of metal resources and
mainly by the sophisticated ability of the Moche metallurgists
in the alloying and surface chemical manipulation processes. AUTHOR CONTRIBUTIONS
By means of empirically optimized methods, they modified at
a nanoscale dimension the surface chemical composition of GI designed the research and wrote the manuscript. GI, MA,
Cu-Au-Ag ternary alloys often containing only small percentages AB, SZ, AF, CG, EM, MP, CR, PS, GD, and LT equally
of precious metals to give them locally an accentuated contributed to preparing the samples, performing the research,

Frontiers in Materials | www.frontiersin.org 11 July 2020 | Volume 7 | Article 230

Ingo et al. Microchemistry of Corroded Gilded Artifacts

analyzing the artifacts, discussing the data, and critically giving CONCYTECH (2009–2011 and 2012–2014). Dr. Erica Isabella
a substantial intellectual contribution. All authors contributed to Parisi is gratefully acknowledged for her technical contribution.
the article and approved the submitted version.

SUPPLEMENTARY MATERIAL
ACKNOWLEDGMENTS
The Supplementary Material for this article can be found
The activities have been carried out in the framework online at: https://www.frontiersin.org/articles/10.3389/fmats.
of the Bilateral Italian–Peruvian project between CNR and 2020.00230/full#supplementary-material

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Materials Australasia, 18 (9), November/December. 7–11.
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artificially produced copper and bronze patina by XPS. Surf. Interf. Anal. 30, the original author(s) and the copyright owner(s) are credited and that the original
135–139. doi: 10.1002/1096-9918(200008)30:1<135::aid-sia720>3.0.co;2-v publication in this journal is cited, in accordance with accepted academic practice.
Schorsch, D. (1988). Silver- and gold- Moche artifacts from Loma Negra, Peru. No use, distribution or reproduction is permitted which does not comply with
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