minerals

Article
The Poopó Polymetallic Epithermal Deposit, Bolivia:
Mineralogy, Genetic Constraints, and Distribution of
Critical Elements
Belén Torres 1 , Joan-Carles Melgarejo 1 , Lisard Torró 2 , Antoni Camprubí 3, *,
Montgarri Castillo-Oliver 4 , David Artiaga 5 , Marc Campeny 1,6 , Esperança Tauler 1 ,
Abigail Jiménez-Franco 1,7,8 , Pura Alfonso 7 and Osvaldo R. Arce-Burgoa 9
1 Departament de Mineralogia, Petrologia i Prospecció Geològica, Facultat de Ciències de la Terra,
Universitat de Barcelona, Carrer de Martí i Franquès s/n, 08028 Barcelona, Catalonia, Spain
2 Geological Engineering Program, Faculty of Sciences and Engineering, Pontifical Catholic University of
Peru (PUCP), Av. Universitaria 180, San Miguel, Lima 15088, Peru
3 Instituto de Geología, Universidad Nacional Autónoma de México, Ciudad Universitaria,
Coyoacán 04510 CDMX, Mexico
4 Australian Research Council Centre of Excellence for Core to Crust Fluid Systems (CCFS) and GEMOC,
Department of Earth and Planetary Sciences, Macquarie University, North Ryde, NSW 2109, Australia
5 Centres Científics i Tecnològics, Universitat de Barcelona, Carrer de Martí i Franquès s/n, 08028 Barcelona,
Catalonia, Spain
6 Departament de Mineralogia, Museu de Ciències Naturals de Barcelona, Passeig Picasso s/n,
08003 Barcelona, Catalonia, Spain
7 Escola Tècnica Superior d’Enginyeria de Mines de Manresa, Universitat Politècnica de Catalunya,
Avinguda de les Bases de Manresa 61–73, 08242 Manresa, Catalonia, Spain
8 Institut de Nanociència i Nanotecnologia (IN2UB), Facultat de Química, Universitat de Barcelona,
Avinguda Diagonal 645, 08028 Barcelona, Catalonia, Spain
9 Colegio de Geólogos de Bolivia, Av. Hernando Siles entre calles 1 y 2, Zona de Obrajes,
Edificio Señor de la Exaltación Nro. 4683, La Paz 8941, Bolivia
* Correspondence: [email protected]; Tel.: +52-55-56224310 (ext. 128)




Received: 19 June 2019; Accepted: 29 July 2019; Published: 31 July 2019


Abstract: The tin-rich polymetallic epithermal deposit of Poopó, of plausible Late Miocene age, is part
of the Bolivian Tin Belt. As an epithermal low sulfidation mineralisation, it represents a typological
end-member within the “family” of Bolivian tin deposits. The emplacement of the mineralisation
was controlled by the regional fault zone that constitutes the geological border between the Bolivian
Altiplano and the Eastern Andes Cordillera. In addition to Sn and Ag, its economic interest resides
in its potential in critical elements as In, Ga and Ge. This paper provides the first systematic
characterisation of the complex mineralogy and mineral chemistry of the Poopó deposit with the
twofold aim of identifying the mineral carriers of critical elements and endeavouring to ascertain
plausible metallogenic processes for the formation of this deposit, by means of a multi-methodological
approach. The poor development of hydrothermal alteration assemblage, the abundance of sulphosalts
and the replacement of löllingite and pyrrhotite by arsenopyrite and pyrite, respectively, indicate
that this deposit is ascribed to the low-sulphidation subtype of epithermal deposits, with excursions
into higher states of sulphidation. Additionally, the occurrence of pyrophyllite and topaz has been
interpreted as the result of discrete pulses of high-sulphidation magmatic fluids. The δ34 SVCDT range
in sulphides (−5.9 to −2.8%) is compatible either with: (i) hybrid sulphur sources (i.e., magmatic and
sedimentary or metasedimentary); or (ii) a sole magmatic source involving magmas that derived from
partial melting of sedimentary rocks or underwent crustal assimilation. In their overall contents in
critical elements (In, Ga and Ge), the key minerals in the Poopó deposit, based on their abundance in
the deposit and compositions, are rhodostannite, franckeite, cassiterite, stannite and, less importantly,
teallite, sphalerite and jamesonite.

Minerals 2019, 9, 472; doi:10.3390/min9080472 www.mdpi.com/journal/minerals

Minerals 2019, 9, 472 2 of 25

Keywords: critical elements; indium; gallium; germanium; tin; silver; low sulphidation; epithermal;
Bolivian Tin Belt

1. Introduction
The Bolivian Andes include important resources in Sn and Ag, minor resources in base metals
as Cu, Zn and Pb, and also in rare metals as In, Ge or Ga, and constitute the famous Bolivian Tin
(Sn–W–Ag–Sb–Bi) Belt [1–5] (Figure 1). An increasing international demand is envisaged for In, Ge
and Ga, particularly in emerging technologies such as the production of photovoltaic cells (In and
Ga), optical fibre and infrared optical technologies (Ge). In addition, these metals are listed as Critical
Raw Materials for the European Union [6], which attests to their strategic importance, particularly
due to the large share in their supply by China—by far, the largest global producer of In, Ga and Ge
in the present time. Consequently, special attention is needed in the mineral characterisation of the
raw materials that carry In, Ga and Ge in the types of ore deposits that are susceptible of harbouring
important resources in such metals.

Figure 1. Regional geological map around the study area, adapted from Reference [7]. The distribution
of the Bolivian Tin Belt was obtained from Reference [2].

In the particular case of Bolivia, the organisation of most mining activities is twofold: it is either
carried out by cooperative organisations grouped into the National Federation of Mining Cooperatives
of Bolivia (FENCOMIN) and that operate by means of traditional and non-industrial methods, or by
the government itself by means of the Bolivian Mining Corporation (COMIBOL), although private
corporations also operate in the country. This complexity in the management of mining activities
in Bolivia results in strong differences in exploitation and exploration strategies and their efficiency
between different mines, let alone the metallurgical processes involved. A critical aspect in which
these activities are in need of assistance is the characterisation of ore bodies, their mineralogy and
Minerals 2019, 9, 472 3 of 25

mineral chemistry or elemental distribution, particularly in the case of critical substances that can
be considered as liabilities or “impurities” in the exploitation and metallurgy of tin or silver, instead
of the subjects for major economic interest that they actually are. Therefore, mineralogical studies
that address such issues are expected to raise awareness on the characteristics of raw material that is
susceptible of mining and, consequently, to provide sound information to better guide the design of
metallurgical processes that maximises the recovery of rare metals.
The Andes cordillera contains four great metallogenic belts. From west to east, these are the Fe,
porphyry Cu–(Mo–Au), Cu–Pb–Zn–Ag, and Sn–(W–Ag–Sb–Bi) belts [3]. The Tin Belt extends between
southeast Peru and the northernmost tip of Argentina, and most of it sits in western Bolivia (Figure 1).
The Oruro region in southwest Bolivia sits on the central part of the Tin Belt, at the hinge between the
northerly NW-SE part of the belt and the southerly N-S part (Figure 1). This region contains some
of the most outstanding tin deposits in the world, which correspond to various types or models of
formation. Among the relatively shallow types of Bolivian deposits, the Poopó deposit was labelled
as a tin-rich low-sulphidation epithermal deposit [8]. Therefore, this deposit can be considered as
one of the representative end-members in the “family” of Bolivian tin deposits. The aim of this paper
is to provide a framework that summarises the mineralogical characteristics and the distribution of
rare metals in this type of deposits. This is a second contribution among a group of papers related to
various Bolivian tin deposits with the same collective aim.

2. Geology
The Poopó deposits are located north and south of the eponymous village, in the Oruro
department, southwest Bolivia. The geographic coordinates of the spot in which the Poopó river crosses
approximately midway of the mineralised structures in this location are −18.381579 and −66.957755.
The Poopó deposits are located near the border between the Bolivian Altiplano and the Eastern Andes
Cordillera, by the NNW–SSE striking Poopó regional fault (Figure 1) and its associated structures [9].
Although no specific studies are available on this subject, it is possible that such a structure is part of a
major crustal discontinuity or a cryptic structural corridor that favoured the emplacement of magmas
and ore deposits as major channelways, similar to other regions in the world in different epochs [10–13].
This fault zone indeed coincides with a major crustal block or domain limit [14–19].
The Eastern Andes Cordillera (EAC) consists of Paleozoic low-grade metasedimentary rocks
(slates, marls, sandstones, shales and quartzites) that were deposited in a broad marine basin. These
were affected during the Miocene by several granitic intrusions with associated ignimbrites. The
rocks of the EAC in the study area are essentially Silurian black shales and sandstones (Figure 1). The
Bolivian Altiplano is a continental foreland basin between the Eastern and the Western Cordilleras that
consists of Cenozoic sedimentary rocks, among which Pleistocene lacustrine deposits, great endorheic
systems with salt flats, and volcano-plutonic complexes associated with the Andean orogeny [20]
are noticeable. The Andean orogeny produced large-scale faults and fold-thrust belts with double
vergence, although the east vergence is dominant [14–19]. The formation of ore deposits in the region
is associated with the Andean orogeny and the concomitant magmatic activity.
The Poopó deposits consist of a vein system along the regional Poopó–Uyuni fault system with
a general N-S strike (Figures 1 and 2). The largest vein in the area developed directly on the main
fault, dips 50–70◦ E, and experienced severe cataclastic deformation due to the fault reactivation
after mineralisation. Ancillary veins around the main one show the same essential strike but milder
deformation and less vertical dipping. The mineralogy of veins is ever dominated by quartz. Most
veins show cataclastic brecciation that was associated with faulting activity, and breccia fragments were
cemented by later hydrothermal mineralisation. Brecciation can also be due to hydrothermal processes
alone, but it is a less common feature than cataclastic brecciation in these deposits. Whether brecciated
or not, all veins show a polyphase and multi-episodic character typical of epithermal deposits. Neogene
intermediate to acid volcanic domes occur in the vicinities of the veins, particularly close to them in
the northern part of the vein system, between the Cóndor Iquiña and Calaveras areas (Figure 2). Such
Minerals 2019, 9, 472 4 of 25

nearness has led to the suggestion that the formation of the veins was triggered by the emplacement of
such domes [1].

Figure 2. Local geological map of the Poopó area, redrawn from Reference [21].
Minerals 2019, 9, 472 5 of 25

3. Methodology
Two sets of mineralised structures were sampled, north and south of the Poopó village. These are
mined by two cooperative entities: the Poopó Cooperative (north) and the San Francisco Cooperative
(south), and were sampled on surface and underground exposures, respectively. The obtained samples
were studied in thin and polished sections by means of transmitted- and reflected-light petrography,
X-ray diffraction (XRD), scanning electron microscopy with energy analyser (SEM-EDS), electron probe
microanalysis (EPMA), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).
With the sole exception of ICP-MS, all the equipment is available at the Centres Científics i Tecnològics
of the Universitat de Barcelona.
The XRD equipment was a PANalytical XPert PRO MPD alpha1 diffractometre with a focaliser
primary monochromator and an Xcelerator detector. The radiation used was Kα1 Cu (λ = 1.5406 Å) at
45 kV and 40 mA. Spectra were interpreted by means of the PANalytical XPert software.
The SEM-EDS equipment was an ESEM Quanta 200 FEI XTE 325/D8395 electron microscope. A
Zeiss Evo microscope with an EDS Oxford INCA detector, available at the Universitat Autònoma de
Barcelona, was also used. Both microscopes were used at 20–25 keV and at a working distance of
10 mm.
EPMA analyses were carried out with a Cameca SX-50 with four WDS spectrometers and EDS at
20 keV and beam current of 15 nA. The analytical programs and standards were pyrite (S, PET, Kα),
FeS2 (Fe, LIF, Kα), Co (Co, LIF, Kα), NiO (Ni, LIF, Kα), GaAs (As, TAP, Lβ), and InSb (Sb, PET, Lβ) for
analyses on arsenopyrite; rutile (Ti, PET, Kα), Fe2 O3 (Fe, LIF, Kα), Nb (Nb, PET, Lα), InSb (In, PET, Lα),
cassiterite (Sn, PET, Lα), and Ta (Ta, LIF, Lα) for analyses on cassiterite; sphalerite (S, PET, Kα), FeS2 (Fe,
LIF, Kα), sphalerite (Zn, LIF, Kα), CdS (Cd, PET, Lβ), and InSb (In, PET, Lα) for analyses on sphalerite;
FeS2 (S, PET, Kα), FeS2 (Fe, LIF, Kα), chalcopyrite (Cu, LIF, Kα), sphalerite (Zn, LIF, Kα), Ge (Ge, LIF,
Kα), GaAs (As, TAP, Lβ), Ag2 S (Ag, PET, Lα), CdS (Cd, PET, Lβ), InSb (In, PET, Lα), cassiterite (Sn, PET,
Lα), InSb (Sb, PET, Lβ), PbS (Pb, PET, Mα), and Bi2 S3 (Bi, LIF, Lα) for analyses on sulphosalts. The
detection limit (d.l.) for each element and the obtained data are displayed in Supplementary Materials
Table S1.
LA-ICP-MS analyses were carried out with a Photon-Machines Excite 193 nm excimer laser system
coupled to an Agilent 7700× ICP-MS mass spectrometer available at Macquarie University Geochemical
Analysis Unit (GAU) (Australia). Calibration of the instrument was done using a NIST610 standard
and the values of Cu and Bi [22]. Each analysis of cassiterite, rhodostannite, stannite and teallite was
normalised to the Sn contents determined by the electron microprobe; whereas sphalerite analyses
were normalised against Zn. The counting time for each analysis was 90 s, including 30 s of background
and 60 s of sample acquisition. In all analysis, the repetition rate of the laser beam was 10 Hz, and
its energy density, 70% (6.5 J/cm2 ). To monitor the accuracy of the measurements, the BCR-2 (Basalt,
Columbia River) standard was also analysed as secondary standard. The samples were analysed in
runs of 15 analyses, comprising 10 analysis of unknowns, bracketed by two analyses of the NIST610 at
the beginning and the end of each run, as well as one analysis of the BCR external standard after the
first set of NIST610. The detection limits for REE, Ba, Rb, Th, U, Nb, Ta, Pb, Sr, Zr, Hf, Ti, Y and Ga span
10 to 20 ppb, for Sc and V 100 ppb, and for Ni 2 ppm. The accuracy for each analysis ranges between 1
wt.% and 10 wt.%, and the spot diameter ranged between 14 and 40 µm. Data reduction was carried
out online by using the GLITTER software [23,24]. The data are displayed in Table 1 (selected elements
In and Ga) and in Supplementary Materials Table S2 (full extent of analysed elements).
Sulphur isotopes analyses were analysed in 85 single grains of sulphide minerals. Pyrite,
chalcopyrite, sphalerite and galena grains were separated by careful hand picking under a binocular
microscope. Samples were analysed with a continuous flow mass spectrometer Delta C Finnigan MAT
coupled with an elemental analyser TC-EA Carlo Erba 1108, at the Centres Científics i Tecnològics of
the Universitat de Barcelona. The results are expressed in the delta notation as per mil deviations of
the Vienna-Canyon Diablo Troilite (VCDT) standard and the standard deviation is determined to be
Minerals 2019, 9, 472 6 of 25

0.2%. The results were calibrated by using the IAEA S1, IAEA S2, IAEA S3 and NBS-123 international
reference standards, and are displayed in Table 2.

Table 1. In and Ga determinations by means of LA-ICP-MS in selected minerals of the Poopó deposit.
All values are reported in ppm. Data selected from Table S2.

Mineral Label 115 In 1σ 69 Ga 1σ

P1-B-32 269 65 110 85
P2-A-37 1030 180 140 35
P2-B-40 2360 170 246 18
P2-C-46 949 84 233 21
P2-D-48 2520 80 340 11
P3-A-49 10,500 340 1360 46
P3-B-52 3640 110 717 22
P3-B-53 5750 190 1280 45
P4-A-67 1120 220 380 75
P4-B-70 779 170 608 120
P4-D-73 1850 390 565 120
P4-E-75 5010 1200 599 140
sphalerite P5-A-77 3230 750 463 110
P6-A-81 360 95 447 110
P6-A-82 457 120 260 74
P7-A-84 1610 110 166 12
P7-B-86 1300 92 289 23
P8-A-88 809 65 478 40
P9-A-93 203 19 246 25
P9-B-96 1850 190 769 85
P9-B-97 307 34 266 31
P10-A-147 269 73 164 46
P10-B-149 1120 380 146 47
P10-C-152 482 200 116 50
P11-B-156 3870 1100 <dl -
P11-C-157 3780 1200 508 100
P1-C-34 368 23 199 13
P2-B-41 2400 200 85.7 7.1
P2-D-47 3140 290 53.8 5.1
P8-B-91 1090 94 0.90 0.094
stannite
P9-A-94 2820 380 10.9 0.96
P10-C-153 2650 1400 46.4 24
P11-C-158 11,100 3200 38.9 13
P11-D-159 8040 2400 22.9 6.5
P4-A-68 6070 1200 377 74
P4-B-69 5160 1000 239 48
rhodostannite P4-D-72 6030 1300 441 95
P4-E-76 5800 1300 316 81
P7-B-87 1240 260 241 10
P5-B-80 10,800 2900 108 23
P8-A-89 1480 120 54.0 6.0
teallite
P8-A-90 1220 98 10.3 2.2
P9-A-95 1460 150 0.76 0.096
P1-B-33 3530 130 24.3 0.38
P2-A-39 3070 110 8.95 1.4
cassiterite
P2-B-42 4280 150 157 16
P10-B-150 18,3000 1900 3060 306
Key: <dl: below detection limits. -: no result.
Minerals 2019, 9, 472 7 of 25

Table 2. Sulphur isotopic composition of sulphides in the Poopó deposit (Bolivia), normalised to the
Vienna-CDT (VCDT) standard.

Sample Mineral δ34 SVCDT (%)

P1 chalcopyrite −4.8
P6 pyrite −3.7
pyrite −3.4
P7
sphalerite −2.8
pyrite −4.1
P8 sphalerite −3.2
chalcopyrite −4.2
pyrite −4.2
P11
sphalerite −5.8
pyrite −4.6
P12
sphalerite −5.5
P13 sphalerite −5.4
pyrite −4.5
P19
galena −5.9
pyrite −5.4
P22
sphalerite −4.6
P23 sphalerite −4.4

4. Mineralogy

4.1. Alteration Assemblages

The extent of hydrothermal alteration around the mineralised structures is very limited (up to
a few cm) and often obscured by late fault reactivations and the subsequent infiltration of meteoric
water. The visible portion of hydrothermal alteration assemblages (no drill cores are available) consists
essentially of “sericite”, quartz, pyrite and pyrophyllite. “Sericite”, due to its crystal sizes (less than
50 µm wide), corresponds to illite or illite-smectite and makes up to 90% (modal abundance) of
altered host rocks, and was previously mapped all along the Poopó–Uyuni fault [21]. Pyrophyllite,
albeit localised, is a conspicuous mineral in these alteration assemblages and occurs as pervasive
replacements of host rocks or in stringers as radial aggregates of up to ~200 µm long crystals in close
association with pyrite, and postdates part of the ore associations (Figure 3A–G). Adularia does not
appear to be an abundant gangue mineral, and occurs as vein material (Figure 3H).

4.2. Mineralogy of the Veins

The veins—both the major ones along the Poopó–Uyuni fault and ancillary structures—are
basically constituted by quartz and sulphides of various types. The mineralisation is characterised by
abundant cataclastic textures. However, quartz shows various primary hydrothermal textures, such as
massive milky aggregates, and banded to comb aggregates, and sulphides may form micro-banding
textures with rhythmic patterns (Figure 4D) but they occur normally as passive or reactive successions
by cavity or fracture lining (Figure 4E,F, Figures 5–8). Three episodes of mineralisation have been
clearly elucidated from the present state of mining operations. In this section, we describe the minerals
found in ore associations within the veins and their interrelationships.
Minerals 2019, 9, 472 8 of 25

Figure 3. Photomicrographs of diagnostic gangue minerals in the Poopó deposit. (A) Pyrophyllite
stringers with pyrite, in pyritised host shales; polarised reflected light. (B) Same as A, but under
transmitted light and crossed polars. (C) Vein material (sphalerite, quartz and pyrite) with later
pyrophyllite and pyrite replacing sphalerite; polarised transmitted light. (D) Same as C, but crossed
polars. (E) Sphalerite stringers in host rocks that underwent strong alteration by pyrophyllite, with
an association of pyrophyllite and pyrite replacing sphalerite through the stringer rims; polarised
transmitted light. (F) Same as E, but crossed polars. (G) Same as E and F, but under polarised reflected
light. (H) Association of tin sulphosalts (franckeite and rhodostannite) and sphalerite, cut by a later
association of fine-grained adularia and pyrite; polarised reflected light.
Minerals 2019, 9, 472 9 of 25

Figure 4. Photomicrographs and back-scattered electron images of selected textural features in the
Poopó deposit. (A,B) Microbrecciation in hydrothermal ore-bearing associations cemented by tin
and silver sulphosalts of Stages 2 and 3; polarised reflected light. For the complete mineralogy of
cementing Sn, Pb and Ag sulfosalts, see Figure 9. (C) Detail of brecciated material cemented by Stage-2
sulphides and sulphosalts; notice the rounded fragments of earlier vein material; back-scattered electron
image. (D) Cyclic micro-banding textures in ore associations of Stage 2; back-scattered electron image.
(E) Arsenopyrite → pyrrhotite → pyrite → sphalerite + sulphosalts succession with the development of
“bird’s eyes” textures due to the replacement of pyrrhotite by pyrite and mascasite; all the sequence is
reactive except for the precipitation of pyrrhotite on arsenopyrite; polarised reflected light. (F) Teallite
and “sericite” in micro-cavities after the precipitation of pyrite and wurtzite (reactive); back-scattered
electron image.
Minerals 2019, 9, 472 10 of 25

Figure 5. Back-scattered electron images of early mineralisation (Stage 1) in the Poopó deposit. (A) Early
arsenopyrite followed by topaz and pyrite, and by a close association between sphalerite and stannite
that formed reactively at the expense of pyrite; sample from the Calaveras section. (B) Apatite and
zircon in close association with early löllingite. (C) Monazite enclosed in apatite in close association
with löllingite, the latter having been almost entirely replaced by arsenopyrite. (D) Thorianite enclosed
in monazite, in association with pyrite that was partly replaced by sphalerite. (E) Similar association to
C, in which arsenopyrite and galena replaced löllingite, that remains as relicts. (F) Inset from E that
shows late micro-aggregates of acanthite crystals in cavities; it is uncertain whether these formed before
or after the replacement of löllingite by arsenopyrite.
Minerals 2019, 9, 472 11 of 25

Figure 6. Polarised reflected light images of ore associations that are rich in tin minerals at the Poopó
deposit. (A,B) Pyrite reactively followed by cassiterite (“needle tin”), passively followed by quartz,
reactively followed by franckeite and these, in turn, by kësterite. (C) Pyrite reactively followed by
franckeite + sphalerite, reactively followed by rhodostannite and kësterite. (D) Pyrite reactively
followed by sphalerite, and reactively followed by rhodostannite. (E) Sphalerite reactively followed by
pyrite, and by stannite + teallite. (F) Close association between sphalerite and teallite.
Minerals 2019, 9, 472 12 of 25

Figure 7. Back-scattered electron images of ore associations that are rich in tin minerals at the Poopó
deposit. (A,B) Micro-cavities or geodes dominantly lined by franckeite; notice that sphalerite in B
occurs earlier in the paragenetic sequence than in A. (C) Franckeite replaced by an assemblage of
rhodostannite, cassiterite and stibnite. (D) Sphalerite replaced by pyrite and galena, and then by
rhodostannite and franckeite. (E) Micro-cavities in quartz lined by bendtite, and banded mineralisation
with mutual intergrowths of quartz, franckeite and stannite. (F) Cylindrite and franckeite followed by
supergene kleemanite and plumbogummite.
Minerals 2019, 9, 472 13 of 25

Figure 8. Back-scattered electron images of ore associations that are rich in lead and silver sulphosalts
at the Poopó deposit. (A to C) Earlier sphalerite, pyrite and cassiterite associations postdated by
jamesonite with later andorite (A), rhodostannite (B) or intergrown with terrywallaceite (C). (D) Acicular
jamesonite crystals with later andorite lining the remaining cavity. (E) Close topaz + arsenopyrite
association (similar to Figure 5A) followed by a close sphalerite + stannite association, and by
canfieldite-lined micro-fractures; sample from the Calaveras section. (F) Andorite + pyrite that
reactively followed sphalerite.
Minerals 2019, 9, 472 14 of 25

Vein Minerals
The mineralogy determined in this study for the Poopó deposits is very complex, as over fifty
species have been identified as part of the vein mineral associations, and their interrelationships can be
rather intricate. “Simple” sulphides and arsenides in the Poopó deposits are sphalerite and wurtzite
[ZnS], pyrite and marcasite [FeS2 ], rhodostannite [Cu2 FeSn3 S8 ], stannite to kësterite [Cu2 (Zn,Fe)SnS4 ],
herzenbergite [SnS], berndtite [SnS2 ], galena [PbS], stibnite [Sb2 S3 ], acanthite [Ag2 S], jalpaite [Ag3 CuS2 ],
greenockite [CdS], bismuthinite [Bi2 S3 ], “stibiobismuthinite” [(Bi,Sb)4 S7 ], teallite [PbSnS2 ], pyrrhotite
[Fe1-x S], cinnabar [HgS], arsenopyrite [FeAsS], and löllingite [FeAs2 ]. Tin sulphosalts are cylindrite
[Pb3 Sn4 FeSb2 S14 ], franckeite [Fe2+ (Pb,Sn2+ )6 Sn2 4+ Sb2 S14 ], and “incaite” [(Pb,Ag)4 Sn4 FeSb2 S15 ] (a
Sn2+ -rich variety of franckeite). Lead, silver and copper sulphosalts are jamesonite [Pb4 FeSb6 S14 ],
andorite [PbAgSb3 S6 ], terrywallaceite [AgPb(Sb,Bi)3 S6 ], treasurite [Ag7 Pb6 Bi15 S32 ], tetrahedrite to
tennantite [(Cu,Fe)12 (Sb,As)4 S13 ], proustite to pyrargyrite [Ag3 (As,Sb)S3 ], canfieldite [Ag8 SnS6 ],
ramdohrite [Ag3 Pb6 Sb11 S24 ], and semseyite [Pb9 Sb8 S21 ]. Besides minerals of the sulphides class,
other minerals in the ore associations in the Poopó deposits are native bismuth [Bi], topaz
[Al2 (SiO4 )(F,OH)2 ], cassiterite [SnO2 ], wolframite [(Fe,Mn)WO4 ], apatite [Ca5 (PO4 )3 ], zircon [ZrSiO4 ],
monazite [(Ce,La,Nd,Th)PO4 ], thorianite [ThO2 ], adularia [KAlSi3 O8 ], siderite [FeCO3 ], kleemanite
[ZnAl2 (PO4 )2 (OH)2 ·3H2 O], and plumbogummite [PbAl3 (PO4 )2 (OH)5 ·H2 O]. All these minerals are
hypogene, with the exception of kleemanite and plumbogummite, which are considered as supergene
minerals. Additional supergene minerals [25] are epsomite [MgSO4 ·7H2 O], kermesite [Sb2 S2 O], and
vivianite [Fe2+ 3 (PO4 )2 ·8H2 O]. Additional hypogene minerals [25] are argyrodite [Ag8 GeS6 ], zinkenite
[Pb9 Sb22 S42 ], and baryte [BaSO4 ]. The interrelations among these minerals can be very complex, with
either passive or reactive sequential precipitation (Figures 4–8).
Sphalerite constitutes the 60% (modal) of mineralisation, which makes of it the most abundant
mineral altogether in the ore, and it occurs in various generations. It occurs generally as anhedral
crystals intergrown with other minerals with very variable sizes (Figure 4C–E, Figure 5A, Figure 6C,F
and Figure 8A,B,E), and with dark colours, which is a common indicator of high XFeS values, as
confirmed from EPMA analyses (see sections below). Sphalerite can be limitedly replaced by small
amounts of fine-grained chalcopyrite, stannite or rhodostannite (Figures 5A and 6D,E) and pyrrhotite.
Its polymorph wurtzite cannot be easily differentiated from sphalerite due to its colour, anhedral
character, and the nearness of their main peaks in XRD spectra. However, wurtzite can be identified
effectively when its euhedral terminations are visible in cavities.
Rhodostannite is the most abundant tin sulphide in the mineralisation as it accounts for 80%
(modal) among such minerals. It occurs as heterogeneous aggregates of brownish to rosy (under
transmitted light) anhedral crystals. Stannite and kësterite are polymorphs and each constitutes its own
isomorphic series with iron-rich end-members, i.e., stannite–ferrostannite and kësterite–ferrokësterite,
all of them within the stannite group of the sulphide class. Kësterite is generally richer in Zn than
stannite and has low anisotropy, whereas stannite is richer in Fe than kësterite, strongly anisotropic,
and distinctly twinned. Such characteristics allowed to determining that the most abundant mineral
from this group in the Poopó deposit is stannite.
Cassiterite accounts for less than 10% (modal) of vein mineral assemblage, and constitutes a major
mineral in the mineralisation. Its crystal quality and shape, and the shape of its aggregates are very
variable, but it is common as interstitial crystals to sphalerite or as “needle tin”, that is, heterogeneously
distributed acicular crystals (Figure 6A,B). Topaz occurs as zoned euhedral crystals, as vein material
(Figure 5A).
Galena, stibnite and acanthite are relatively scarce minerals in this deposit, as most of the lead,
antimony and silver appear to be concentrated preferentially in sulphosalts rather than in “simple”
sulphides. These minerals are commonly associated with suphosalts with similar cationic content,
essentially Ag, Ag-Pb, Pb, and Sn-Ag sulphosalts. Similarly, canfieldite occurs in association with Sn
sulphides or Sn-Ag sulphosalts, generally in fractures as a late mineral (Figure 8E). Bismuthinite, a rare
mineral in the deposit, is found as replacements after native bismuth.
Minerals 2019, 9, 472 15 of 25

Löllingite is a trace mineral in the deposit as it only occurs as relict grains within replacive
arsenopyrite. However, its pseudomorphosed crystals can be identified as prismatic, euhedral, and
up to 1 mm long (Figure 5E,F). Arsenopyrite can be locally abundant in the deposit and it may
occur in different generations as euhedral crystals up to 100 µm in diameter, and found forming
massive monomineralic aggregates. It is considered to be a relatively early mineral in each particular
association (Figure 5) as is commonly crosscut by other minerals. The replacement of pyrrhotite
by pyrite and marcasite occurred with the development of “bird’s eyes” textures (Figure 4E). These
minerals determine a löllingite → (reactive) arsenopyrite → (passive) pyrrhotite → (reactive) pyrite
sequence that is characteristic of early stage 2.
Cylindrite and franckeite are the most characteristic tin sulphosalts of the Poopó district
(Figures 6 and 7), and are conspicuous to the point that cylindrite was first described in this locality [26].
Cylindrite is quite visible in hand specimens as radial aggregates of long cylindrical crystals in cavities.
Franckeite is a common mineral in the Poopó deposits but rather rare in other localities. It occurs
commonly as >500 µm wide tabular crystals in association with other minerals (especially cylindrite,
sphalerite, rhodostannite, stannite and kësterite; Figures 6 and 7) or as massive aggregates. Both tin
sulphosalts occur late in the mineral associations, typically lining micro-fractures (Figures 6 and 7).
Jamesonite is abundant in the paragenesis, and occurs as prismatic crystals up to 300 µm long with
well-developed shapes in cavities, but also as massive aggregates or lining micro-fractures (Figure 8).
Andorite is another characteristic mineral in these deposits and can be locally abundant as elongated
crystals or as massive aggregates lining cavities (Figure 8). Terrywallaceite is typically associated with
jamesonite, even replacing it or intergrown with it (Figure 8C). The rest of the numerous sulphosalt
species are relatively rare minerals and their space interrelations are less clear than the above.
Among phosphates, apatite and monazite are relatively rare in the mineralisation (Figure 5).
Monazite is closely associated with (even rarer) thorianite. Kleemanite and plumbogummite occur
as late minerals in the paragenetic sequence, likely as supergene products of Zn and Pb minerals
(Figure 7F).

4.3. Paragenetic Sequence

Three stages of mineralisation can be characterised from this study (Figure 9), based in the
interrelations of ore minerals, provided that no crosscutting relations between macroscopic structures
were macroscopically observed: (1) an association dominated by quartz, pyrite, arsenopyrite, sphalerite
and cassiterite (Zn-Sn stage), (2) an association of tin sulphides and sulphosalts (Sn stage), and (3) an
association of antimony, lead and silver sulphosalts (Ag-Pb stage). As explained above, the character
of the mineralisation was determined by periods of activity of the Poopó–Uyuni fault. Therefore,
Stage 1 is essentially represented by breccias with fragments that vary in size (mm- to cm-sized) and
shape (generally rounded). Pre-brecciation associations are mostly fine-grained, and coarsen in open
cavities. This stage may consist of euhedral quartz, cassiterite and pyrite, and a later association
in which sphalerite replaced pre-existing cassiterite. Stage 2 was preceded by some activity in the
Poopó–Uyuni fault and is characterised by open-space lining textures (i.e., comb or cockade growth)
in which most sulphides occur along with tin sulphosalts. As already noticed in previous work [27],
stannite is relatively scarce and rhodostannite, cylindrite and franckeite were formed in its stead. Stage
3 has a replacing character with respect to previously formed minerals (especially those of Stage 2),
and is dominated by jamesonite and concentrated silver minerals.
Besides such general behaviour, part of the mineralisation in the northern part of the district (the
Calaveras section; Figure 2) contains topaz (Figure 5A), wolframite, bismuthinite, and apatite, with
accessory monazite, zircon and thorianite (Figure 5B–D) as vein material in close association with
sulphides, arsenides and sulphosalts.
Minerals 2019, 9, 472 16 of 25

Figure 9. Paragenetic sequence obtained in this study for the Poopó deposit. Notice critical
element-bearing minerals highlighted in red (most abundant or richer in those elements) and orange
(less abundant or poorer in those elements).

5. Mineral Chemistry
The use of EPMA allowed to systematically characterising the elemental distribution in ore
minerals (Table S1). Sphalerite in the Poopó deposit attains XFeS values up to 0.18 (18 wt.%), high
Cd (up to 1 wt.%), and low In contents (up to 0.5 wt.%). Fe and Ti contents in cassiterite are below 1
wt.%, whereas Ta contents are about 0.2 wt.%. Arsenopyrite crystals are strongly zoned due to their
variable Sb contents (up to 5 wt.% Sb), whereas its Co and Ni contents rarely exceed 1 wt.%. The As
contents in arsenopyrite are systematically greater than those of S, and amount between 28.9 wt.%
and 31.8 wt.% As. In the absence of pyrite during the precipitation of arsenopyrite, which was formed
as the replacement of löllingite, these compositions correspond to temperatures that range between
~170 ◦ C and ~325 ◦ C (Figure 10).
Stannite is up to 0.45 wt.% Ag, and also rich in Ge, Se, Cd and In, with contents that range between
0.13 wt.% and 0.47 wt.%. Besides sphalerite and stannite, other minerals with relatively high cadmium
contents are franckeite, rhodostannite, jamesonite, andorite and terrywallaceite, perhaps due to partial
replacement of greenockite from Stage 2. Franckeite, cylindrite and rhodostannite can also be relatively
rich in silver; rhodostannite may attain 4.6 wt.% Ag, thus nearing the stoichiometric composition of
toyohaite [Ag2 FeSn3 S8 ].
Minerals 2019, 9, 472 17 of 25

Figure 10. Arsenopyrite geothermometry based on the pseudobinary T-X diagram of Reference [28]
for the Poopó deposits. The range of temperatures was obtained by using the EPMA analysed of
arsenopyrite in Table S1, plotted against the arsenopyrite + arsenic/löllingite boundary considering (1)
the absence of pyrite in association with arsenopyrite, (2) the sequence that determines that löllingite
was replaced by arsenopyrite, and (3) pyrrhotite was passively precipitated on arsenopyrite, and then
replaced by pyrite. The löllingite → arsenopyrite → pyrrhotite → pyrite sequence denotes an increasing
availability of sulphur in the environment or a temperature rise (e.g., Figure 16 in Reference [5]). Key:
Apy = arsenopyrite, As = native arsenic, L = liquid, Lö = löllingite, Po = pyrrhotite, Py = pyrite.

As of EPMA analyses, relevant indium contents were found in franckeite, rhodostannite, sphalerite,
cassiterite and stannite, but only traces of gallium were found. EPMA values and guidelines from
References [29–33] allowed to selecting the most susceptible minerals to contain relevant amounts of
strategic elements indium and gallium, which were considered to be sphalerite, cassiterite, stannite
and rhodostannite. The most noticeable germanium contents were consistently obtained by means of
EPMA in rhodostannite (up to 0.21 wt.% Ge) and franckeite (up to 0.16 wt.% Ge), and this element was
also quantified in bismuthinite, terrywallaceite, jamesonite, stannite, treasurite, and in unidentified
minerals (Table S1). Other strategic elements, such as tantalum, were also analysed in cassiterite, with
contents averaging 0.2 wt.% Ta (Table S1), which are comparable to those in other occurrences in the
world with soundly determined magmatic origins [34–37].
LA-ICP-MS analyses yielded very variable contents in indium and gallium, by means of the
quantification of 115 In and 69 Ga (Figure 11, Table 1 and Table S2). Such contents are up to 10,500 ppm
In (>1 wt.% In) and 1360 ppm Ga (>0.1 wt.% Ga) in sphalerite, up to 183,000 ppm In (18.3 wt.% In)
and 3060 ppm Ga (>0.3 wt.% Ga) in cassiterite, up to 11,100 ppm In (>1.1 wt.% In) and 3200 ppm
(>0.3 wt.% Ga) Ga in stannite, up to 10,800 ppm In (~1.1 wt.% In) and 108 ppm Ga in teallite, and up
to 6070 ppm In (>0.6 wt.% In) and 441 ppm Ga in rhodostannite. The two minerals with apparent
higher contents in In (cassiterite and rhodostannite) are those with lower and more erratic contents in
Ga (except in rhodostannite), whereas the mineral with the apparent lower contents in In (sphalerite)
shows the higher contents in Ga (Figure 11). With the exception of the peak In and Ga contents in
rhodostannite, such contents behave much alike those in teallite.
Minerals 2019, 9, 472 18 of 25

Figure 11. As, Ag, Ga, Sn, In and Cd contents in key minerals cassiterite, teallite, rhodostannite, stannite
and sphalerite of the Poopó deposit as per LA-ICP-MS determinations. See data for critical elements In
and Ga in Table 1 and for all elements in Table S2.

6. Sulphur Isotopes
Sulphur isotope determinations were carried out on 17 sulphide (sphalerite, galena, chacopyrite
and pyrite) samples from the Poopó deposit. δ34 SVCDT values range between −5.9% and −2.8%
altogether, and most values occur within a narrow range between −6 and −4%. δ34 S values range
between −5.4% and −3.4% in pyrite, between −5.8% and −2.8% in sphalerite, between −4.8% and
−4.2% in chalcopyrite, and −5.9% in galena (Table 2 and Figure 12).
Minerals 2019, 9, 472 19 of 25

Figure 12. Histogram of the isotopic composition of sulphur in sulphides of the Poopó deposit, Bolivia.
See data in Table 2.

7. Discussion

7.1. Type of Deposit and Conditions of Formation

The dominantly cataclastic character of textures in the Poopó deposit is due to the contemporaneity
between the activity of the Poopó–Uyuni fault and the mineralisation processes in the associated veins
(Figure 4A–C). Such dominantly structural brecciation was cemented by new material of hydrothermal
origin and could have controlled the polyphase and multi-episodic character of the mineralisation.
Therefore, it is interpreted that the successive stages of mineralisation were closely associated with the
activity of the Poopó–Uyuni fault. Based on the mineralogy determined in this study, we can endorse
the interpretation that the Poopó deposits correspond to the Sn-rich low-sulphidation epithermal
type, as formulated in Reference [8]. In particular, the abundance of löllingite pseudomorphs and
arsenopyrite, and the occurrence of pyrrhotite (replaced by pyrite) place this deposit in the “classical”
low-sulphidation field, as of Reference [37]. However, the occurrence of pyrophyllite indicates
the entrainment of relatively high-temperature fluids of the high-sulphidation type, as typically
occurs between the roots of epithermal deposits and porphyry-type deposits [38,39]. However,
pyrophyllite can also be stable down to 100 ◦ C when water is supersaturated in silica, but still at low pH
conditions [40]. The occurrence of topaz in epithermal deposits is not uncommon either, particularly in
association with high to intermediate sulphidation fluids in the magmatic–epithermal transition or
in deep hypogene advanced argillic alteration assemblages [41–44]. The low pH of fluids and high
temperature that the occurrences of pyrophyllite and topaz entail is in apparent disagreement with the
dominantly low sulphidation character of the mineralisation, which includes the occurrence of (A)
the löllingite → arsenopyrite reactive sequence followed passively by the pyrrhotite → pyrite reactive
sequence, (B) the occurrence of abundant Ag, Pb or Sn sulphosalts, and (C) the occurrence of adularia
and “sericite”, either in the alteration assemblages or as vein material. Nevertheless, the occurrence
of minerals that were formed at a relatively low pH in low- to intermediate-sulphidation epithermal
deposits should not be shocking anymore [41]. In the Poopó case, it would be necessary to trace in
detail the occurrence of pyrophyllite and topaz and their possible association with a temperature
anomaly in the deposit. Such an anomaly would be most likely located on a preferential channelway for
the upwelling of mineralising fluids along the Poopó–Uyuni fault, as is common in low to intermediate
sulphidation deposits [41], and could constitute a form of telescoping. Detailed fluid inclusion and
O and H stable isotope studies would be the ideal complement for such purpose. However, it is
relevant to notice that the northern half of the mineralised structures, in which topaz occurs as vein
material (Calaveras section, north of the Poopó village; Figure 2), lies beside a group of Miocene
hypabyssal intrusive bodies with associated tourmalinisation (dacitic porphyries at the Cóndor Iquiña
area; Figure 2) [21]. Such occurrence further highlights the likeliness for a proximal magmatic source
for mineralising fluids, and thus it may spearhead the influx of magmatic fluids. This, in turn, suggests
Minerals 2019, 9, 472 20 of 25

a possible elemental and mineralogical zonation of this deposit that would make an interesting topic
for further studies.
Pyrophyllite and adularia do not occur in the same mineral associations and no temperature
or pH evolution can thus be deduced from their occurrence. However, pyrophyllite and pyrite
formed after early sphalerite in Stage 1 (sphalerite I in Figure 9), in reactive succession (Figure 3A–G),
which implies a low-pH and high-fluorine incursion during the early ore stages, which evolved from
relatively sulphur-deprived and low sulphidation fluids that originated the löllingite → arsenopyrite
→ pyrrhotite → pyrite sequence. The possible formation of pyrophyllite (thus, a low pH environment)
in the midst of an overwhelmingly low-sulphidation environment may represent an excursion of low
pH fluids similar to those explored in Reference [41].
The occurrence of adularia in epithermal deposits is commonly associated with boiling, whether
in association with the precipitation of ore minerals or not [41]. The association between adularia
and the formation of ore deposits is not clear at Poopó (Figure 3H), probably due to the scarcity
of this mineral in comparison to other low-sulphidation epithermal deposits elsewhere. No other
minerals or textural evidence that are suggestive of boiling have been found in the deposit, and thus
the relevance of different mechanisms for ore formation can only be derived from further studies.
Provided that the space distribution of adularia in each boiling event is anything but homogeneous [41],
it would be possible to find this mineral abundantly in deeper portions of the deposit. Therefore, the
known mineralisation at Poopó could correspond to the upward and lateral outflow carapace around
the boiling areas (similar to Figure 11 in Reference [41]). Such possibilities will constitute starting
hypotheses for future studies in this area.
The composition of arsenopyrite (with As contents greater than S contents) denotes low sulphur
fugacity conditions during the precipitation of this mineral. However, arsenopyrite was predated by
löllingite, which remains as relicts and was mostly consumed to form arsenopyrite (Figure 5E). The
löllingite → arsenopyrite sequence indicates an increase in state of sulphidation, either by an increase
in sulphur fugacity or a decrease in temperature. A similar evolution occurs next in the paragenetic
sequence with the replacement of pyrrhotite by fine-grained pyrite and marcasite, as shown by the
occurrence of “bird’s eyes” textures (Figure 4E). Therefore, the löllingite → arsenopyrite → pyrrhotite
→ pyrite represents a sequence toward higher states of sulphidation within the low sulphidation field,
at the beginning of Stage 2. Such an excursion toward higher states of sulphidation does not compare
to the one described above for early Stage 1 and does not necessarily have a genetic meaning, but it
remains a trend worth testing in further studies when it comes to the characterisation of the behaviour
of mineralising fluids. Interestingly, it has been noted that (A) an increase in pH and H2 S activity, (B) a
decrease in chlorine content (that is, a decrease in salinity of mineralising fluids), and (C) a decrease in
temperature through conductive cooling have a role in increasing the primary indium saturation in
mineralising fluids, particularly in the sphalerite–roquesite solid solution [45]. Otherwise, enrichment
in indium may be produced by diffusion through earlier Fe-rich sphalerite, at decreasing pH and
salinity, and increasing S2 fugacity in mineralising fluids [45].

7.2. Sources for Sulphur

The sulphur isotope composition (δ34 SVCDT ) of sulphides in Poopó ranges between −5.9% and
−2.8%, which is similar to those in several deposits of the central Andean tin belt, particularly those
from the Santa Fe and Huanuni districts [46], in other tin deposits elsewhere [47], and in intermediate-
to low-sulphidation epithermal deposits in Cordilleran environments [48–50]. In such cases, hybrid
sources for sulphur are suggested as most likely, in which part of the sulphur would come from
magmatic sources (either from a direct contribution or by scavenging of sulphur from magmatic
rocks) and another part would from sedimentary or metasedimentary sources. This idea would be
supported by (A) the dominantly metasedimentary host rock assemblage in the Poopó deposits, and
(B) the likeliness of magmatic-hydrothermal incursions into the mineralising system, as suggested
by the occurrence (1) of pyrophyllite in deep hypogene alteration assemblages and (2) of topaz as
Minerals 2019, 9, 472 21 of 25

vein material, besides the nearness of the deposits to possibly coetaneous hypabyssal and volcanic
rocks (see section above). Another possibility is that the values obtained in this study account for
purely magmatic sources for sulphur. This possibility can be sustained as long as parental magmas
included a component of crustal assimilation; otherwise, sulphur would come from magmas that
were generated after partial melting of sedimentary rocks. Such is precisely the case of the magmas
associated with Cenozoic tin mineralisation of the Eastern Andean Cordillera, which resulted mostly
from sediment melting in a thickened continental crust, and yield a distinctive peraluminous and
reduced signature, thus belonging to the S-type, ilmenite-series [51–53]. The most likely magmatic
source for sulphur and other geological elements for the mineralisation would come from the Late
Miocene Morococala volcanic complex (Figure 1, [2]) and associated rocks. Both cases would result in
significantly decreasing δ34 S values below the “typical” magmatic values around 0% [54]. Therefore,
whether it is one possibility or the other, a magmatic source for sulphur is envisaged as the main
contributor to the formation of sulphides in the Poopó deposit. However, part of the sulphur is likely
to have been inherited from sedimentary or metasedimentary sources anyway.

7.3. Distribution of Strategic Elements in the Deposit

Besides the endowment in Sn and Ag of the Poopó epithermal deposit, the occurrence in it of
strategic elements such as In, Ga and Ge deserves special attention in order to provide sound guidelines
for exploration and mining endeavours in the area. No indium minerals like petrukite, roquesite, indite,
laforetite, abramovite, or sakuraiite were found, and similarly with gallium and germanium. These
elements were only found in traces within minerals in which they are not part of the stoichiometric
norm. Therefore, indium occurs in noticeable contents in franckeite, rhodostannite, sphalerite, teallite,
cassiterite and stannite as of EPMA and LA-ICP-MS analyses, and is up to ~18 wt.% In in cassiterite, a
major mineral in the deposit. High indium contents also occurred in stannite, sphalerite and teallite
(up to ~0.11 wt.% In).
Gallium contents were determined to be up to 3060 ppm Ga by means of LA-ICP-MS in cassiterite
of Stage 3, although EPMA analyses were not apparently promising and also recorded the lowest
obtained contents (Figure 11). However, the minerals in which the gallium content ranged less
variably were sphalerite and rhodostannite (Figure 11), despite not having recorded peak contents in
this element.
Although it was not found in this study, the occurrence of argyrodite [25] attests to the occurrence
of germanium in the Poopó deposit. In this study, germanium contents hit a maximum in rhodostannite
(up to 0.21 wt.% Ge), although its interspecific distribution was wider than those of indium and
gallium, as it is also a noticeable element in franckeite, bismuthinite, terrywallaceite, jamesonite,
stannite-kësterite, treasurite, and some unidentified minerals.
Therefore, the key minerals with relevant contents in critical elements In, Ga and Ge in the Poopó
deposit, based on their abundance in the deposit and compositions are rhodostannite, franckeite,
cassiterite, stannite and, less importantly, sphalerite and jamesonite. Interestingly, such minerals occur
all along the paragenetic sequence: rhodostannite, jamesonite, teallite and terrywallaceite in Stage 3,
franckeite, stannite-kësterite and bismuthinite in Stage 2, and cassiterite and sphalerite in Stages 1 and
2. Furthermore, this study illustrates the need for evaluating the likeliness of high contents in strategic
elements beyond “typical” bearers such as sphalerite or cassiterite.

8. Conclusions
The Sn- and Ag-rich polymetallic low-sulphidation epithermal deposits of Poopó in southwest
Bolivia are circumscribed to the Bolivian Tin Belt and occur in a major regional boundary between the
Andean Altiplano and the Eastern Andes Cordillera. Such boundary is represented by the Poopó–Uyuni
fault, which constitutes the main mineralised structure in these deposits. It is likely that the formation
of these deposits is linked to the activity of the Late Miocene Morococala volcanic complex.
Minerals 2019, 9, 472 22 of 25

This study represents the first systematic characterisation to be made available about the Poopó
deposits. The morphology of these deposits, their mineralogical characteristics, interrelations and
evolution of alteration and ore associations allow us to endorse earlier characterisations of the Poopó
deposits as a Sn- and Ag-rich low-sulphidation epithermal deposit. However, despite such endowment,
these deposits may bear a major potential in strategic elements.
The studied deposits display very complex mineralogy and interrelations among the constituting
minerals, which can be grouped into three consecutive stages of mineralisation. Stage 1 is described as
a Zn-rich stage that includes the localised occurrence of topaz and pyrophyllite. Stage 2 is described
as a Sn-rich stage with tin sulphides and sulphosalts. Stage 3 is described as an Ag-Pb-rich stage
with numerous sulphosalts of either or both metals. Both in Stages 1 and 2 the early minerals draw
mineralogical sequences towards increasing states of sulphidation in ore associations (arsenopyrite to
pyrite, or löllingite to arsenopyrite to pyrrhotite to pyrite).
The occurrences of pyrophyllite (in the alteration assemblage) and topaz (vein mineral association
in Stage 1) stand out as indicators of low pH fluids at relatively high temperatures (high sulphidation)
as mineralising fluids, although the Poopó deposits and the mineral associations contained in them are
mostly circumscribed to the low-sulphidation type among epithermal deposits. Fluids associated with
the deposition of pyrophyllite and topaz may have spearheaded the input of magmatic fluids through
long-lasting preferential channelways for the ascent of hydrothermal fluids, which is a possibility that
calls for attention in further studies.
The range of variation of δ34 SVCDT values in sulphides of the Poopó deposit suggests either mixed
magmatic and sedimentary or metasedimentary sources for sulphur, or dominant magmatic sources
after magmas that underwent significant crustal assimilation or, plainly, S-type magmas.
Strategic elements In, Ga and Ge (as of EPMA and LA-ICP-MS determinations) occur in noticeable
amounts in several minerals of the Poopó deposits, among which rhodostannite, franckeite, cassiterite,
stannite-kësterite, teallite (all of them tin minerals), sphalerite and jamesonite are major contributors
due to both their abundance along the paragenetic sequence and their contents in such metals.
Less importantly, bismuthinite, terrywallaceite and treasurite also have significant Ge contents.
Rhodostannite and jamesonite (plus terrywallaceite) occur in Stage 3, franckeite and stannite-kësterite
(plus bismuthinite) in Stage 2, and cassiterite and sphalerite in Stages 1 and 2; therefore, minerals with
affinity for In, Ga and Ge occur through the entire paragenetic sequence.

Supplementary Materials: The following are available online at http://www.mdpi.com/2075-163X/9/8/472/s1,

Table S1: EMPA. Table S2: ICP-MS.
Author Contributions: Conceptualization: J.-C.M., L.T., A.C., O.R.A.-B., P.A.; fieldwork: B.T., J.-C.M., L.T., D.A.,
A.J.-F.; methodology: B.T., J.-C.M., L.T., M.C.-O., D.A., M.C., E.T., P.A.; writing—original draft preparation: B.T.,
A.C.; writing—review and editing: A.C., J.-C.M., L.T., M.C.-O.
Funding: This study benefitted from the budged granted by the Generalitat de Catalunya (Autonomous
Government of Catalonia) to the Consolidated Research Group SGR 444, the AECID project A3/042750/11, CCD
project 2015-U008, and the Peruvian CONCYTEC-FONDECYT-World Bank project 107-2018. Additional funding
was provided by the ARC Centre of Excellence for Core to Crust Fluid Systems (CE110001017), as well as by the
Fundació Pedro Pons (UB), and by the Instituto de Geología (UNAM) by means of its yearly personal budget
allocation. Part of the analytical data were obtained using instrumentation funded by DEST Systemic Infrastructure
Grants, ARC LIEF, NCRIS/AuScope, industry partners and Macquarie University.
Acknowledgments: The National Federation of Mining Cooperatives of Bolivia (FENCOMIN) gave permission to
the authors to access the studied mines and to perform the necessary sampling; all individuals from FENCOMIN,
Juan Elvys Trujillo from the Universidad Técnica de Oruro, and local miners are cordially thanked for their kind
and efficient help. Technical assistance was kindly provided by Xavier Alcobé, Maria Barba (XRD), Eva Prats,
Aránzazu Villuendas (SEM-EDS), Xavier Llovet (EPMA), all of them at the Centres Científics i Tecnològics of the
Universitat de Barcelona. The authors would like to acknowledge William L. Griffin and Suzanne Y. O’Reilly for
their scientific insight, and William Powell, Yoann Gréau, Rosanna Murphy, Olivier Alard and Sarah Gain for their
help with the LA-ICP-MS analyses at the GAU (Macquarie University). This is contribution 1374 from the ARC
Centre of Excellence for Core to Crust Fluid Systems (http://www.ccfs.mq.edu.au) and 1326 in the GEMOC Key
Centre (http://www.gemoc.mq.edu.au).
Conflicts of Interest: To the knowledge of the authors, no conflict of interest whatsoever exist between them and
any other individuals with regard to the contents of this paper. The funders had no role in the design of the study,
Minerals 2019, 9, 472 23 of 25

in the collection, analyses, or interpretation of data, in the writing of the manuscript, or in the decision to publish
the results.

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