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Understanding Exotic-Cu Mineralisation: Part II - Characterisation of Black

Copper (Cobre Negro) ore

Conference Paper · August 2015

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Understanding Exotic-Cu Mineralisation: Part II -
Characterisation of Black Copper (Cobre Negro) ore
Andrew Menzies, Eduardo Campos, Victor Hernández, Sebastian Sola, Rodrigo Riquelme
Departamento de Ciencias Geológica, Universidad Católica del Norte, Antofagasta, Chile
Monserrat Barraza
CISEM (Centro de Investigación y Servicios Mineralógicos), Universidad Católica del Norte, Antofagasta, Chile
Abstract. Exotic-Cu deposits often form in the vicinity of
the parental porphyry system due to the lateral migration
of Cu-bearing fluids. Mineralisation in this type of deposit
comprises different species of copper minerals and
mineraloids broadly defined as green- and black-copper
ores. The analysis and subsequent definition of Cu-
bearing minerals from exotic-Cu deposits is extremely
complex due to the fine scaled textures and
compositional variation. This is particularly true for so-
called “black-copper” minerals. The QEMSCAN®
analysis of a large suite of samples from such deposits
has enabled a detailed list of definitions encompassing
the variability of both Cu-wad and Cu-pitch, specifically
related to the Mn concentrations, as well as numerous
sub-ordinate elements such as Mg, Al, Fe, Si, P, Ca, P,
Cl, and S. The confirmation of these definitions has
enabled the correlation between physical ore
characteristics (i.e. colour and texture) with known
mineralogy. In addition, QEMSCAN® analyses of exotic-
Cu deposits yield more accurate and precise Cu-
mineralogy and Cu-deportment, which is especially
relevant to plant mineral processing samples.
Keywords. Exotic-Cu, Black Copper, Cobre Negro,
Cu-Wad, Cu-Pitch, QEMSCAN, El Tesoro
1 Introduction
The central Andes of northern Chile and southern Perú
is well known for hosting a premier copper province
with exceptional metal endowment contained in
numerous deposits, some of which are amongst the
world´s largest copper deposits (e.g. Chuquicamata, La
Escondida) (Sillitoe, 2013). A distinctive feature
observed in the Atacama Desert is the occurrence of
exotic supergene Cu-mineralisation that is spatially and
genetically related to porphyry systems, whch are the
source of the metals (Münchmeyer, 1996, Sillitoe,
2005).
Exotic-Cu deposits can be formed in the vicinity of
the parental porphyry system when lateral migration
component of the Cu-bearing solutions occurs, in
response to topographically driven groundwater flow
(Münchmeyer, 1996), in which case, copper oxide
mineralisation (mainly chrysocolla with minor
atacamite, copper-pitch and copper-wad) will be
deposited in the surrounding paleodrainage network as
interstitial cement in permeable gravels sequences or
impregnation along fractures and pores in older
basement rocks. The exotic-Cu deposits varies widely
in size and can reach up to 3.5 million tons of fine Cu,
with Radomiro Tomic, El Tesoro, Spence, Mina Sur, and
Lomas Bayas as some of the most important examples
in northern Chile (Münchmeyer, 1996). Mineralisation
in this type of deposits comprises different species of
copper minerals and mineraloids broadly defined as
black-copper and green-copper ores, colloquially known
as “cobre negro” and “cobre verde”, respectively.
Black-copper ores are poorly understood and roughly
can be characterized as amorphous or poorly crystalline
Cu-bearing oxides, showing variable chemical
composition. These mineral phases occur closely
related to supergene oxide copper minerals such as
chrysocolla atacamite, chalcantite, antlerite and
brochantite, the green-copper ore minerals, which are
described separately in Campos et al. (2015). The most
commonly associated gangue minerals are limonites,
kaolinite, quartz, sericite, chlorite, plagioclase and
feldspar. Typically, sulphides are not present in exotic-
Cu deposits.
2 Methodology
A selection of samples from four deposits in northern
Chile were analysed using automated mineralogy
techniques (QEMSCAN®) housed at CISEM,
Universidad Católica del Norte, Antofagasta, Chile.
These samples comprise various rock fragments ranging
from 2 – 10 cm in size. The larger samples were cut
with a diamond tipped saw and analysed on the
unpolished surface, whilst, the smaller samples were
mounted in resin, and polished prior to analysis. All
samples were carbon coated prior to analysis.
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. 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). Multiple analyses were made at different pixel
spacing resolution, most commonly 10, 5 or 2 μm to
observe the fine-scaled textures. The back scattered
electron levels were calibrated from 0-255 where Quartz
= 42, Copper = 130, and Gold = 232.
3 Historical Definitions in the QEMSCAN® mineral list contains numerous sub-
definitions of various specific minerals, for example, Cu-
There have been numerous studies of exotic-Cu sulphides contains definitions for chalcopyrite, bornite,
deposits in Chile, and a general observation of these chalcocite and so forth, each of which has a fixed
results clearly indicate the variability of Cu- structure and thus relatively narrow major and minor
mineralisation and of the definitions used (see Table 1 as element composition. In contrast, the definitions for the
an example). This is problematic when trying to “black copper” minerals has been subdivided in various
evaluate mineralogy and for metallurgical processing, groups, namely, Cu-Pitch, Cu-Mn Pitch, Cu-Wad and
specifically using modern techniques such as Cu-Mn Wad. Furthermore, each group has, in some
QEMSCAN®. This is further compounded by the use cases, up to 50 subgroups to accurately capture the
of non-specific generic mining terminology, such as variability of the Cu and Mn concentrations and their
“black-copper” ore. Black copper ore has been association with various other minor elements commonly
subdivided into various descriptive subgroups, for present. Such classifications are important and
example copper pitch and copper wad (e.g., Fam, 1979; necessary if the QEMSCAN® results are to be used for
Pincheira et al., 2003). Copper pitch a silica-rich Cu- the calculation of elemental concentrations and
bearing phase closely associate to chyrsocolla, (and elemental mineral deportment.
often called “black chrysocolla”), whereas copper wad The group labelled “Cu-Other” in Figure 1 is a “trap”
is primarily Cu-bearing manganese oxyhydrates. classification that represents any Cu-bearing spectrum
Reghezza (2002) uses even more specific subgroups, that does not classify in the other groupings. This is
such as wad-type substances, black copper oxides, most likely due to the presence of minor or trace
polymetallic oxides/silicates, and (Fe, Cu). In either elements (or combinations of both) that have yet to be
case, all of these are generic terms but not clear captured in the definition, or a mixed spectrum from the
definitions. boundary between two phases, which is common in
In addition to these definitions of variable Cu and Mn these samples given the fine-scaled (micron level)
concentrations, it should be noted that Cu-Wad is textures and banding (Figure 1 and 2).
commonly amorphous showing characteristics similar to The complex and variable nature of the Cu-Mn pitch
cryptomelane (K1-2(Mn3+,Mn4+)8O16·XH2O), birnessite and Cu-Mn wad is evident in Figure 1 (from El Tesoro)
(K0.33Mn3.9+7O14·7H2O), and crednerite (CuMnO2) (Mote and Figure 2 (from Mina Sur).
et al., 2001; Cuadra and Rojas, 2001). Furthermore, it Sample AHM-ET-001 from El Tesoro (Figure 1)
was noted by Pincheira et al. (2003) that the Cu-Wad, displays a range of mineralogy, predominantly Cu-
whilst containing Cu and Mn in significant quantities, halides (e.g. atacamite), Cu-carbonates (e.g. malachite),
could also have Fe, Si, and Al as major or minor Cu-silicates (e.g. chrysocolla) and variable compositions
concentrations as well as Ca, Na, K, Cl, P, Pb, Zn, Mg, of Cu-Mn pitch and Cu-Mn wad, all of which form
S, P, Mo, Co, As, U, V and Ni as minor or trace different bands of variable thickness, and sometimes on
elements. Table 1 presents a selection of the historical an extremely fine-scale (10 – 100 µm). The Cu-Mn wad
definitions of Cu-Wad from the literature. and Cu-Mn pitch occur in discrete zones within these
bands, predominantly as globules or inclusions. In
addition, there is no obvious preferred mineral
Table 1. A selection of the definitions of Cu-Wad in the associations, with both the Cu-Mn wad and Cu-Mn pitch
literature. occurring in contact with Cu-carbonate, Cu-silicate or
Location Cu-halide.
Definition Reference
(Chile) Sample VH-MS-002-B from Mina Sur (Figure 2) is
Mny Cux Oz El Abra Moraga (2000) similar. However in this case the Cu-Mn pitch and Cu-
Huinquintipa, Mn wad forms as continuous bands as well as discrete
2CuO MnO2 Garcia et al. (2007)
Collahuasi zones of globules.
Cuadra and Rojas
CuMnO2 Radomiro Tomic
(2001)
The elemental maps clearly show the variability of
Rojas and Müller concentrations for Cu, Mn and Si, and easily
CuO·MnO2·7H2O Damiana
(1994) discriminate the fine-scaled textures. Furthermore, the
Cu-rich Mn-Fe oxides Mina Sur Münchmeyer (1996) association of Fe and Ca with Cu-Mn pitch and Cu-Mn
Cu-bearing Mn Damiana, Quebrada wad is clearly observable. Figure 2 is a EDS spectrum
Mote et al. (2001)
oxyhydrates, Turqueza which highlights the presence of minor elements in the
Variable Mn, Fe, Cu, Si Cu-Mn pitch, in this case specifically Mg, Al, S, Cl, Ca
Mina Sur Pincheira et al. (2003)
and Al
and Co.
A detailed analysis of numerous samples from
various deposits indicates that a cut-off of approximately
4 Results 10 wt% Si can be used for distinguishing between
“pitch” and “wad”. Furthermore, the wad and pitch
One of the benefits of QEMSCAN® is its ability to
definitions have numerous sub-groups. This is primarily
present mineralogical information at various levels of
based on the presence of Mn, which is then further
detail. In particular QEMSCAN® field scans highlight
subdivided based on the ratio of Cu to Mn as well as the
the complex variability of the so-called “black-copper”
incorporation of detectable levels of Fe, Ca, S, Si, P and
ore.
Cl amongst others. Whilst these definitions may be
It should be noted that each of the mineral definitions
somewhat arbitrary, it does aid in defining critical groups
for QEMSCAN® analysis, and thus ultimately for 5 Discussion and Conclusions
mineralogical interpretation, Cu concentrations, and Cu
mineral deportment, all critical parameters for modelling QEMSCAN® is a powerful automated mineral
and metallurgical processing. Furthermore, these groups analytical technique that uses the combined information
do appear to be texturally correct and correspond to from the BSE and low count EDS X-ray signals.
macro observations (colour changes) and BSE imaging. Standard mineral database classifications used in the
QEMSCAN® system can be improved and / or
Mineral Name expanded
Area % depending on the analytical requirements and
Area
Background the information
0,74 19198 requested. Such a process is laborious
Cu-Sulphides 0,00 1
1 cm Cu-Oxides and 0,04
requires1002careful calibration to confirm any new
Cu-Halides classifications.
13,25 345879 This is particularly true for minerals that
Cu-Carbonates
Cu-Sulphates
can 49,90
display
0,00
1302577
a wide
0
range of variable compositions. In
Cu-Phosphates the case
0,00 of Cu-mineralisation
25 updated classifications are
Cu-Silicates 18,23
Cu-Pitch
required
1,63
to 475797
enable
42654
accurate and precise determinations of
Cu-Mn Pitch Cu mineralogy,
4,95 129182 Cu concentrations and Cu deportment, as
Cu-Wad
Cu-Mn Wad
well 0,00
as
3,94
the 54
occurrence
102818
of minor elements, such as Mn.
Silicates+Cu These0,26are important
6658 factors in the mineral processing
Fe-Oxides+Cu 0,04 969
Cu-Other
and plant
7,35
quality
191823
control and monitoring. This study
Fe-Oxides presents
0,01 updated132 classifications for the Cu-Mn pitch and
Calcite 0,08 2058
a Apatite
Cu-Mn 0,05
wad 1232
minerals associated with exotic-Cu
Others mineralisation.
0,29 7464

i. The analysis and subsequent definition of Cu-bearing

minerals from exotic-Cu deposits is extremely complex
due to the compositional variations, particularly for so-
called “black-copper” minerals, namely Cu-pitch and
Cu-wad.
ii. The QEMSCAN® analysis of numerous samples from
a variety of locations in northern Chile has enable a
b c detailed list of definitions encompassing the variability
of both Cu-Mn wad and Cu-Mn pitch, specifically
related to the Mn concentrations, as well as numerous
sub-ordinate elements such as Mg, Al, Fe, Si, P, Ca, P,
Cl, and S.
iii. The application of these definitions is complicated by
the very fine-scale textures observed, commonly
micron scale banding, and the presence of inclusions,
d e or globules.
iv. These definitions improve QEMSCAN® analysis, and
consequently mineralogical interpretation, Cu
concentrations, and Cu deportment for exotic-Cu
deposits.
v. Further analysis using trace elements and the analysis
of samples from other exotic-Cu deposits will aid in
refining and confirming the application of these
definitions.
f g
Acknowledgements
Figure 1. QEMSCAN® (a) Mineral Map, (b) BSE Image, (c)
Cu, (d) Mn, (e) Si, (f) Fe and (g) Ca elemental concentrations The authors wish to acknowledge the support of the staff
for sample AHM-ET-3A (El Tesoro). Field of view is at CISEM (Centro de Investigación y Servicios
approximately 3 cm. See text for a description of the mineral Mineralógicos) at the Universidad Católica del Norte,
groupings used in the QEMSCAN® Mineral Maps legend. Antofagasta, Chile who supported this project by
Elemental concentrations vary from 0 (black) to 100% (bright providing sample preparation and QEMSCAN®
colour); where the element is not detected the colour is grey.
The elemental concentrations are primarily relative, with the analytical time; specifically Marina Vargas, Monserrat
brighter “colour” representing a higher concentration. The raw Barraza, Pamela Fonseca and Carolina Ossandon. This
BSE image has had the brightness adjusted by +25% to ongoing research has also been supported by
improve observed variations. FONDECYT project 1121049 and LMI-COPEDIM.
 References
1 cm Mineral Name Area % Area
Background Campos 0,74 E, Menzies
19198 A H, Hernandez V, Sola S, Barraza, M, and
Cu-Sulphides 0,00
Riquelme R 1(2015), Understanding Exotic-Cu Mineralisation:
Cu-Oxides 0,04 1002
Cu-Halides
Part
13,25
I - 345879
Characterisation of Chrysocolla, 13th SGA meeting,
Cu-Carbonates Nancy.
49,90 This volume.
1302577
Cu-Sulphates Cuadra,0,00 P. & Rojas,
0 G. (2001) Oxide mineralization at the
Cu-Phosphates 0,00
Radomiro 25
Tomic porphyry copper deposit, northern Chile.
Cu-Silicates 18,23 475797
Cu-Pitch
Econ.
1,63
Geol., vol. 96, pp. 387-400.
42654
Cu-Mn Pitch Fam, 4,95
R. (1979)
129182Mineralización de cobre del tipo exótico en el
Cu-Wad norte
0,00 de Chile.
54 Actas II Congreso Geológico Chileno, Arica.
Cu-Mn Wad 3,94 2, 102818
Tomo pp. C235-C263.
Silicates+Cu
Fe-Oxides+Cu
Garcia0,26
0,04
6658
C, Garcés969
J, Rojas C Zárate G (2007) Efecto sinérgico del
Cu-Other tratamiento
7,35 de mezclas de minerales conteniendo copper wad y
191823
Fe-Oxides sulfuros
0,01 secundarios.
132 Hydrocopper 2007, VI International
Calcite 0,08
Copper 2058
Hydrometallurgy Worshop, 16-18 Mayo, Viña del Mar
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Moraga (2000) Un modelamiento mineralógico en el yacimiento El
Abra, Tipo Porfido Cuprifero. XI Congreso Geologico
Chileno, Vol 1, sesión temática N°2, pp. 298-392.
Mote, T.I., Becker, T.A., Renne, P. & Brimhall, G. (2001)
Chronology of exotic mineralization at El Salvador, Chile, by
40Art/39Ar dating of copper wad and supergene alunite. Econ.
Geol., vol. 96, pp. 351-366.
Münchmeyer, C. (1996) Exotic deposits: products of lateral
migration of supergene solutions from porphyry copper
deposits. In Camus, F., Sillitoe, R.H. & Petersen, R. (eds.),
Andean copper deposits: New discoveries, mineralization,
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b c Münchmeyer, (1994) Los Depósitos Exóticos: Productos de
Migración Lateral Asociada a Sistemas Porfíricos. 7º Congreso
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Reghezza, (2002) Criterios de discriminación para caracerización
de cobres negros. CODELCO Internal Report. 7 pgs.
Pincheira, M., Kelm, U., Helle, S, Dagnino, A, and Osses, M.
(2003) Las fases de cobre negro en yacimientos ex’oticos:
nuevos antecedentes mineralógicos, texturales y
composicionales. Minerales, Vol 58, Num 253, pp. 13-18.
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d e Sillitoe, (2005) Supergene Oxidized and Enriched Porphyry
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f g

Figure 2. QEMSCAN® (a) Mineral Map, (b) BSE Image, (c)

Cu, (d) Mn, (e) Si, (f) Fe and (g) Ca elemental concentrations
for sample VH-MS-002-A (Mina Sur). Field of view is
approximately 3 cm. See text for a description of the mineral
groups used in the QEMSCAN® Mineral Maps legend.
Elemental concentrations vary from 0 (black) to 100% (bright
colour); where not detected the element is grey. The elemental
concentrations are primarily relative, with the brighter “colour”
representing a higher concentration. The raw BSE image has
had the brightness adjusted by +25% to improve observed
variations.

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