OLOGI C
GE A
la serena
Automated mineralogical analysis of archaeological
samples from northern Chile: Case Study I – pre-Hispanic
copper mining in the Collahuasi district, region Tarapacá
Andrew Menzies*1, Valentina Figueroa2, Benoît Mille3, Diego Salazar2, Hans Wilke1, Pia Sapiains1, Pamela Fonseca4
and Carolina Ossandon4
1. Departamento de Ciencias Geológicas, Universidad Católica del Norte, Avenida Angamos 0610, Antofagasta, Chile
2. Instituto de Investigaciones Arqueológicas y Museo R.P. Gustavo Le Paige, Universidad Católica del Norte.
3. UMR 7055 Préhistoire et Technologie, Nanterre, France & Centre de Recherche et de Restauration des Musées de
France, Paris, France.
4. CISEM (Centro de Investigación y Servicios Mineralógicos), Universidad Católica del Norte, Antofagasta, Chile
* email: amenzies@ucn.cl
Summary. The analytical investigation of archaeological
samples is of importance to understanding the social
environment and technological capacity of the various
cultures through time. In addition, comparisons between
regions provide details as to technological advancements
and how this information is disseminated as well as
confirming contact and trade. The application of automated
mineralogy to this field adds an extra level of information
normally not applied by providing fast and detailed
mineralogical information of samples thus allowing
investigating features such as homogeneity vs inclusions,
massive vs disseminated textures, trace mineral
identification, mineral grain sizes, and elemental
deportment. Such information is able to confirm similarities
or differences between materials or compounds used for
various artefacts. In this example, samples of Cu-bearing
ores from various metallurgical furnace production sites are
analysed to confirm the mineralogy of the source rocks.
The samples are from the late pre-Hispanic times in the
district of Collahuasi, in northern Chile. The classification of
these samples provides a baseline for comparison with
other products, such as slags, to confirm the possible
technological metallurgical process applied. In addition, it
also provides information on the probable sources for the
ore.
Keywords: QEMSCAN®, Archaeology, pre-Hispanic, Cu-
Ore, Collahuasi, Tarapacá, Chile
Introduction
The investigation of archaeological samples in northern
Chile is of importance to understand the social
environment and technological systems of the various
cultures through time. The ability to correctly classify
various artefacts enables comparisons between regions and
through time to be clearly distinguished. The application
automated mineralogy to this field adds an extra level of
information normally not commonly applied.
The samples on the mining-metallurgical production in late
pre-Hispanic times in the district of Collahuasi, in northern
Chile. This area is located approximately 4500 meters
above sea level, with little agricultural potential, but,
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significantly, with important copper resources. This study
presents the automated mineralogical results of 11 samples
from the metallurgical furnaces located at Ujina 8, Ujina
10 and from the Collahuasi 37 settlement. The
pyrometallurgical structures were built in stone and
oriented perpendicular to the direction of the dominate
winds (Mille et al., 2013). All samples are from the late
pre-Hispanic times and detailed radiocarbon dating is
currently in progress (Figueroa, 2015). The north of Chile
is well known for its copper resources and in the Altiplano
region of Tarapacá, the mining district is located Dona Inés
de Collahuasi (Sillitoe, 2005). The majority of these
deposits are Cu-porphyries with variable and diverse
copper mineralogy. Over the last decade, automated
mineralogy (QEMSCAN®) has been routinely applied to
aid in understand the Cu-mineralogy and improving
metallurgical mineral processing (e.g. Menzies et al., 2015;
Campos et al., 2015).
Sample Description
The samples are from three archaeological sites in northern
Chile that show evidence of indigenous mining and
metallurgical activities, namely Site 1 - Collahuasi-37
(Co37) (Romero and Briones, 1999), Site 2 - Ujina 8
(Uj8), and Site 3 - Ujina 10 (Uj10) (Salazar et al., 2013a,
2013b). These sites are comprised of numerous sectors
with evidence of pre-Hispanic smelting places, which are
grouped into two types of basic features: concentration of
metallurgical slag surface; and stone furnaces (Salazar et
al., 2013a, 2013b; Figueroa, 2015). The 11 samples were
selected because they had visible Cu mineralisation in
hand specimen.
Analytical Methodology
Each sample, which was between 1 and 3 cm in size, was
mounted in 30 mm circular briquettes using epoxy resin.
The briquettes were then cured, polished and carbon
coated prior to automated mineralogical analysis at CISEM
(Centro de Investigación y Servicios Mineralógicos),
 SIM 5 GEOPATRIMONIO

Universidad Católica del Norte (UCN), Antofagasta, Chile.

The analyses were made using a QEMSCAN® model
E430, which is based on a ZEISS EVO 50 Scanning
Electron Microscope (SEM) combined with Bruker Series
4 energy dispersive spectrometer (EDS) detectors. Routine
analysis is performed with a spot size of less than 1 μm at
an operating voltage of 25 kV and a beam current of 5 nA.
The standard 1000 counts per point were acquired and this
yields a detection limit of approximately 2 wt% per
element for each mineral classification point.
Measurements were performed using iMeasure v5.3.2 and
data reduction using iDiscover v5.3.2. The samples were
analysed in Fieldscan mode at a field size of 1500 μm
(approximate magnification of 50x) or 2500 μm
(approximate magnification of 30x). Multiple analyses
were made at different pixel spacing resolution, most
commonly 10, 5 or 2 μm to determine modal mineralogy
as well as observe the fine-scaled textures. The back
scattered electron levels were calibrated from 0-255 where
Quartz = 42, Copper = 130, and Gold = 232. Examples of
detailed QEMSCAN® analysis of Cu-bearing samples can
be found in Menzies et al. (2015) and Campos et al.
(2015).

Mineral analysis can be carried out using a number of

different operating modes, but in this study the ore samples
were compositionally mapped using the fieldscan
operating mode (Figure 1). In this operating mode, the
electron beam is rastered across the sample at a predefined
stepping interval (which can range from sub-micron levels
upwards, but typically the analysis is carried out between 5
and 20 microns) and at each analysis point an X-ray Mineral Name
Background
Area %
0,43
Area
39

spectrum is measured. Silver Minerals

Cu-Sulphides
0,00
0,00
0
0
Cu-Oxides 0,19 17
Cu-Halides 0,26 24
Cu-Carbonates 0,49 45
Results Cu-Sulphates
Cu-Phosphates
8,08
0,00
735
0
Cu-Silicates 4,21 383
Cu-Mn Pitch 0,00 0

The 11 samples were selected because they had visible Cu Cu-Mn Wad
Cu-Wad
0,00
0,23
0
21

mineralisation in hand specimen. Analytical results Silicates+Cu

Fe-Oxides+Cu
15,44
0,10
1405
9

confirm this and examples of the modal mineralogy Cu-Other

Fe-Oxides
2,32
0,01
211
1

backscattered electron images and elemental maps are

Calcite 0,00 0
Apatite 0,00 0
Quartz 63,39 5770
given in Figure 2, 3, and 4. It is apparent that the samples Muscovite
Plagioclase
2,66
0,00
242
0

display a wide range of Cu-mineralogy (as well as gangue Feldspar

Barite
1,78
0,01
162
1

mineralogy), which ranges from a minimum of 35 % up to Others 0,83 76

a maximum of over 90%. For example, samples Co37-
m10-j, Uj8-m6-c, UjN-m2-b and UjN-m2-e are dominated
by Cu-sulphates (predominantly brochantite), whilst
samples UjN-m1-a, and Uj8-m6-d are dominated by Cu-
carbonates (predominantly malachite). A range of other
Cu-bearing minerals were also detected in variable
concentrations, for example Cu-silicates (chrysocolla), Fe-
oxides+Cu, and Cu-sulphides. Elemental maps are useful
for identifying the presence of certain elements that may
not be known as to which mineral phase they are
occurring, or if only as a trace phase within the various
identified minerals, which may be important for
identifying the mineralogy of key trace elements, for
example, Ag, or As (Figure 3 and 4).
Figure 1. Schematic diagram outlining how the QEMSCAN®
fieldscan measurement mode systematically measures the entire
area of the sample. First row: images of the samples as collected.
Second row: Image of samples mounted in resin, polished, carbon
coated, and placed in a block-holder; waiting to be analysed in
QS31 housed at CISEM. Third row: polished briquette is
separated into pre-defined fields; each field overlaid with a pre-
defined grid of pixels; an x-ray spectrum and backscatter value
are acquired for every pixel and classified by the SIP database to
enable the assignment of mineralogy and chemical composition.
Fourth row: a false colour map is created for each field where
each colour represent a specific mineral or chemical grouping;
the fields are combined to generate a single mosaic of the
analysed area that can be processed and investigated with the
iDiscover software.

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 AT 4 Impacto de las GeocIencIas en la socIedad

In these samples, silver sulfosalts (acanthite, as well as

various Cu-bearing silver minerals, possibly stomeyerite,
mckinstryite or jalpaite) were clearly identified in sample
Co37-m11-b, and to a lesser extent in samples Co37-m12-
b and Uj8-m6-b (Figure 3c). In contrast, As elemental
maps indicate that the As is predominantly incorporated
into a variety of minerals as a minor or trace element, but
does also occur as discrete mineral phases (Figures 5).

A large number of copper ore fragments have been

discovered during the first field excavations. Examination
of the fragments shows that they were carefully
beneficiated to achieve a very high-grade copper ore, as
confirmed by the QEMSCAN® mineralogical analysis.
The results indicate that 3 minerals are clearly
predominant, namely brochantite, malachite and
chrysocolla, with respect to Cu-mineralisation (Figure 2).
The next step will be to relate the archaeological ore pieces
to their precise provenance within the Collahuasi district.

Figure 3. QEMSCAN® results for sample Co37-m11-b.

Clockwise from top left: (a) Mineral Map (sample is
approximately 3 cm in maximum dimension), (b) detailed
mineral map of red rectangle (field of view is 1500 µm); (c) BSE
image, (d) Ag element map; and, (e) Cu element map. Mineral
groupings and colours as per the legend in Figure 5. Elemental
concentrations vary from 0 (black) to 100% (bright colour);
where the element is not detected the colour is grey. The
elemental concentrations are primarily relative, with the brighter
“colour” representing a higher concentration.

Figure 2. Top: Modal mineralogy grouped by Cu-bearing

mineral groups and common gangue minerals. Bottom: Cu-
deportment by Cu-bearing mineral groups. Mineral groups and
colours as per the legend in Figure 5.
Figure 4. QEMSCAN® results for sample UJ8-m8-a.
Clockwise from top left: (a) Mineral Map (sample is
approximately 3 cm in maximum dimension), (b) detailed
mineral map of black rectangle (field of view is 1500 µm); (c) As
element map. Comments as per Figure 3. Mineral groups and
colours as per the legend in Figure 5.

369
 SIM 5 GEOPATRIMONIO

Discussion and Comments Acknowledgements

For its part, the evidence recovered in the mining- The authors wish to acknowledge the support of CISEM
metallurgical Collahuasi district were subjected to various (Centro de Investigación y Servicios Mineralógicos) at the
archaeometric analysis in order to identify the reduced Universidad Católica del Norte, Antofagasta, Chile who
minerals, metallurgical processes and metallic copper provided sample preparation and QEMSCAN® analytical
produced. Combined with PIXE, optical microscopy and time; specifically Marina Vargas and Monserrat Barraza.
SEM-EDS techniques, the results of the study of This project was supported under Proyecto Fondecyt
technology and organization of pre-hispanic Collahuasi 11130651, Laboratorio Internacional Asociado CNRS LIA
copper production will be able to be evaluated in the MINES ATACAMA and PICS NEODESERT.
context of known Inca settlements systems for the study
area. Future work will include analysing a larger suite of References
samples to confirm preliminary observations and confirm
the mineralogical variations between localities. In Campos, E., Menzies A. H., Hernandez V., Sola S., Barraza, M., and
Riquelme R., 2015. Understanding Exotic-Cu Mineralisation:
addition, slags from these localities will be analysed. This Part I - Characterisation of Chrysocolla, 13th SGA meeting,
will provide a re large base-line of information that will be Nancy.
useful, not only for this immediate study, but for
comparative purposes with studies that incorporate Figueroa, V., 2015. Informe Año 1. Proyecto Fondecyt N°11130651.
samples from different areas or at a different time-period.
Knappett, C., Pirrie, D., Power, M.R., Nikolakopoulou, I., Hilditch,
J., Rollinson, G.K., 2011. Mineralogical analysis and
Mineral Name Area % Area provenancing of ancient ceramics using automated SEM–EDS
analysis (QEMSCAN@): a pilot study on LB I pottery from
Background 0,43 39 Akrotiri, Thera. J. Archaeol. Sci. 38 (2), 219–232.
Silver Minerals 0,00 0
Cu-Sulphides 0,00 0 Menzies, A.H., Campos E., Hernández V., Sola S., Riquelme, R.,
Cu-Oxides 0,19 17
2015. Understanding Exotic-Cu Mineralisation: Part II -
Characterisation of Black Copper (“Cobre Negro”) ore, 13th
Cu-Halides 0,26 24 SGA meeting, Nancy.
Cu-Carbonates 0,49 45
Cu-Sulphates 8,08 735 Mille, B., Salazar, D., Bourgarit, D., Figueroa, V., Perlès, C.,
Cu-Phosphates 0,00 0 Berenguer, J., 2013. Emergence of large scale copper production
during the Early Bronze Age in Saint-Véran (France) and in
Cu-Silicates 4,21 383
Prehispanic Northern Chile: a comparative research program.
Cu-Mn Pitch 0,00 0 The Crucible (Neswletter of the Historical Metallurgical Society)
Cu-Mn Wad 0,00 0 (84), 8-9.
Cu-Wad 0,23 21
Silicates+Cu 15,44 1405 Romero, A., and Briones, L., 1999. CO-37: Estado y planificación
inca en Collahuasi (Provincia de Iquique, I región, Chile).
Fe-Oxides+Cu 0,10 9 Estudios atacameños N° 18: 141- 154.
Cu-Other 2,32 211
Fe-Oxides 0,01 1 Salazar, D. Berenguer, J. Vega, G. 2013a. Paisajes minero-
Calcite 0,00 0 metalúrgicos incaicos en Atacama y en el Altiplano Sur de
Tarapacá (Norte de Chile). Chungara, Revista de Antropología
Apatite 0,00 0
Chilena 45: 83-103.
Quartz 63,39 5770
Muscovite 2,66 242 Salazar, D., Figueroa, V., Mille, B., Carrión, H., Balestro, F.,
Plagioclase 0,00 0 Berenguer, J., 2013b. Informe minero-metalúrgico:
Feldspar 1,78 162 prospecciones, excavaciones y análisis. Informe Año 3, Proyecto
Fondecyt N° 1100905.
Barite 0,01 1
Others 0,83 76 Sillitoe, R. H., 2005. Supergene oxidized and enriched porphyry
copper and related deposits. Economic Geology 100th
Anniversary Volume, p: 723-768.
Figure 5. QEMSCAN® mineral list as presented in all
previous figures.

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