MINERALOGIA POLONICA

Vol. 36, No 1, 2005

PL ISSN 0032-6267

Jimena CUCURELLA1, Claudio CANUT DE BON1, María Eugenia CISTERNAS2

PYROBITUMEN RELATED TO SILVER-COPPER DEPOSITS

IN A CRETACEOUS VOLCANIC-SEDIMENTARY SEQUENCE:
TALCUNA DISTRICT, COQUIMBO, CHILE

A b s t r a c t . In recent years, hydrocarbons have been observed in some stratabound copper deposits in
the Cretaceous volcanic-sedimentary sequences in north and central Chile. At the “21 de Mayo” and
“Socavon 2001” mines in the Talcuna district in north-central Chile (29°30’–29°45’ S/70°45’–71°00’ W),
pyrobitumen is associated with ore minerals in Lower Cretaceous rocks. In this district, recent investigations
demonstrate that the ore mineralization, traditionally regarded to be of stratabound (manto) type, has both
structural and lithological controls. Paragenetic relations reflect a hydrothermal emplacement of both
the pyrobitumen and the ore and gangue minerals, while isotopic analyses suggest an organic marine
provenance of the former. Reflectivity 2.0–2.4% indicates the maturity of the pyrobitumen. Its occurrence is
spatially related to sulphide mineralization (chalcopyrite, bornite, chalcocite) and to barren zones, especially
in the walls of fractures and faults that were channels for post-ore diorite dikes. Organic matter was probably
hydrothermally mobilized from limestones of the Arqueros Formation and precipitated first in the ore zones
and then in fractured post-ore dikes. Hydrothermal fluids sealed in calcite and barite related to the
pyrobitumen reveal homogenization temperatures ranging from 180 to 320°C and salinities from 6.5 to
21 wt.% NaCl equivalent. These data characterize the mineralization as a moderate- to low-temperature
event involving fluids of considerable salinity.

Key-words: pyrobitumen, copper stratabound deposit, Lower Cretaceous volcaniclastics, Chile

INTRODUCTION

The presence of bitumen and its metallogenic connection with Cu-Ag mineralization
in Early Cretaceous stratified units were recently described in Chile. Bitumen deposits
occur both in sedimentary rocks, e.g., at Uchumí in Coquimbo (Wilson, Zentilli 1997),
and in volcanic sequences, e.g., at El Soldado in central Chile (Zentilli et al. 1994, 1997;
Wilson, Zentilli 1997) and in the Copiapo district (Cisternas et al. 1999).
The present study is focused on the characteristics of the pyrobitumen found in two
mines in the volcanic-clastic continental sequence of the Quebrada Marquesa For-

1 Facultad de Ingeniería, Departamento de Minas, Universidad de la Serena. La Serena, Chile;

email: jcucurel@userena.cl; canutdebon@netexpress.com

2 Instituto de Geología Aplicada, Universidad de Concepción, Concepción, Chile;

email: mcistern@udec.cl
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mation (QMF): “21 de Mayo” and “Socavon 2001”, located in the Talcuna district, Co-
quimbo. In these mines, copper mineralization, mainly comprising bornite, chalcopyrite
and chalcocite, is both vein type and manto type. The geology of the district was described
by Boric (1985) and Camus (1986). The physico-chemical conditions of the hydrothermal
mineralization have been inferred by the authors from a study of fluid inclusions in
gangue minerals that are associated with the ore minerals and the pyrobitumen.

GEOLOGICAL SETTING

The copper deposits of the Talcuna district (29°30’–29°45’ S/70°45’–71°00’ W) occur

in the Quebrada Marquesa Formation (Aguirre, Egert 1965). The QMF is a sequence of
andesitic lavas and epiclastic and pyroclastic continental rocks deposited in a tectonic
basin close to the coeval magmatic arc. It marks the transition from marine volcanic
conditions of the Arqueros Formation (AF) to a continental environment of the Viñita
Formation (VF) that discordantly overlies the AF (Aguirre, Egert 1965).
Both the AF and QMF were intruded by an Upper Cretaceous (K-Ar 89–108 Ma)
batholith and small stocks assigned to the Late Cretaceous — Early Tertiary. These
stocks also cut the VF (Moscoso et al. 1982). Around the intrusive rocks, hydrothermal
alterations are well developed.
In the Talcuna district, the QMF is represented by a 1500-m sequence of breccias,
lapilli tuffs, andesites and tuffaceous sandstones, containing small intercalations of
calcareous sandstones and shales. The whole sequence is crosscut by ENE to NE
trending diorite dikes.

MINERALIZATION CONTROLS

At the “21 de Mayo” and “Socavon 2001” mines, mineralization occurs in banded
and brecciated (hydraulic and collapse) veins with copper, lead and silver sulphides.
The mined ore contains 1–2% Cu, 0.1–0.5% Pb and 15–30 ppm Ag. There are two main
mineralization controls: NNW trending normal faults that were the feeder channels for
the mineralizing fluids, and a stratigraphic-lithologic position that confines the econo-
mic zones to the intervals where these feeder channels intersect the most “receptive”
units, e.g., the lapilli tuffs.
The upper limit of the mineralization is an iron-manganese bed that acted as a barrier
to the circulating fluids. The manto- and the vein-type mineralized zones are cut by an
NE-NNE system of dextral-normal faults and displaced as a result at 10–100 m.

PYROBITUMEN OCCURRENCES

Pyrobitumen was found both in mineralized and barren zones. In the mineralized
zones, it is associated with the sulphide minerals and intergrown with calcite, barite
22
and zeolites. In the barren zones, bitumen is mainly located in the dikes and at vein
intersections.
Pyrobitumen related to ore zones. Thin and polished sections were used in morpho-
logical observations and helped interpret the paragenetic sequence. The pyrobitumen is
black, amorphous (isotropic), brittle, exhibits vitreous lustre and displays conchoidal
fracture. It occurs in angular fragments, small veins and irregular masses among the
sulphides (Fig. 1).

Fig. 1. Intergrowths of chalcopyrite (grey), calcite (white) and pyrobitumen (black) in a brecciated vein.
Magn. 40x

In the brecciated veins, the pyrobitumen is fractured and forms irregular masses. In
the banded veins, it is attached to their walls or intergrown with the ore minerals.
In both cases, it coexists in simple intergrowths with bornite and chalcopyrite, and with
chalcocite that replaces other sulphide minerals, but is also of hydrothermal origin.
The pyrobitumen is also intergrown with barite, calcite and zeolites that occur in
veins, fractures and vugs in the mineralized zones. These gangue minerals fill con-
traction cracks that developed in the bitumen during its solidification (Fig. 2).

Fig. 2. Stilbite (white) in the solidification contraction cracks of pyrobitumen (black). Magn. 40x
23
 Pyrobitumen related to barren zones. Fine particles of this pyrobitumen mostly occur as
masses in open fractures. They can be found mainly at the intersections of the NNE
trending dikes with stratified rocks, both in their walls and in small feather veins.

PYROBITUMEN ANALYSIS

Reflectance. Reflectance is one of the most useful parameters describing maturation

of organic matter. It is directly applicable to the study of the thermal history of
petroleum and provides a continuous numerical scale that measures the process of ma-
turation and metamorphism (reflectance increases with structural ordering of organic
matter). In the present study, reflectance was measured in two briquettes prepared
from pyrobitumen fragments according to the random procedure. The measured R0 is
equivalent to the percentage of light reflected under the microscope without polarizer.
In both briquettes, the reflectance of 30 particles was measured.
The reflectance values obtained (Table 1) range between 2.0 and 2.4% and suggest
that the organic matter was subjected to a moderate thermal alteration.

TABLE 1

Reflectance of pyrobitumen

No. of data Mean Minimum Maximum Standard deviation

30 2.196 2.041 2.417 0.081

Isotope data. The isotopic determinations were conducted at Actlabs Ltd., Canada.
The average d13C value for the bitumen is –28.8‰. As marine organisms that utilize
carbon dioxide rather than HCO3– to build their cellular material produce a significant
deficiency in d13C due to photosynthesis (Hunt 1979), d13C values between –25 and
–30‰ strongly suggest a photosynthetic origin of the organic matter studied. The-
refore, this value is consistent with an organic marine origin for the carbon and
the supposition that the bitumen was formed by the maturation and destruction of
hydrocarbons which had migrated into the rock fractures.
In addition, a d34S value of –18.4‰ determined in bornite is compatible with
bacterial sulphate reduction that provided the sulphidic sulphur.
Trace elements. The analyses were made using ICP/MS (Total Digestion method) at
Actlabs Ltd., Canada. The most significant trace element in the pyrobitumen (Table 2) is
sulphur (~0.5%). The copper content (149 ppm) is consistent with the close association
between the pyrobitumen and the copper sulphides, while the high silver content
(6.0 ppm) can be explained by the fact that native silver is found filling open spaces.
The analyses also reveal high barium contents (1990 ppm), reflecting a close relation
between the pyrobitumen and barite veins.
The pyrobitumen contains 34 ppm of vanadium. Although this is not a very high
value, it can be related to copper lead vanadate (mottramite) associated with oxide
24
 TABLE 2

Trace elements present in pyrobitumen (ppm)

V 34.0 Ce 2.26 Tm 0.034

Co 2.0 Pr 0.25 Yb 0.22

Th 0.05 Nd 1.08 Ba 1 990

U 0.19 Sm 0.27 Pb 16.0

Y 2.7 Eu 0.053 As 11.0

Zr 3.0 Gd 0.27 Sr 67.0

Nb 0.2 Tb 0.05 Ag 6.0

Sb 0.6 Dy 0.33 Zn 26.0

Lu 0.037 Ho 0.07 Cu 149.0

La 1.23 Er 0.23 Ni 5.0

Ta 0.03 Hf 0.1 S 0.156%

copper minerals found nearby (1.5 km to the NE). Domeyko noted the presence of this
vanadate in 1845 in his “Elements of Mineralogy” (Domeyko 1903). The pyrobitumen
also contains appreciable amounts of lead, zinc and arsenic.

FLUID INCLUSIONS

Fluid inclusions were examined in calcite and barite, the gangue minerals present in
the veins. The calcite samples were collected from the Mercedes Vein in the “21 de
Mayo” mine and the Anita Vein in the “Socavon 2001” mine, while the barite samples
from the Vein No. 5 in the “21 de Mayo” mine and the Vein No. 2 in the “Socavon 2001”
mine (Figs 3, 4).
Fluid inclusions in calcite. Only the biphase primary inclusions (L+V) were studied.
They exhibit regular, oblong to rounded shapes.
The homogenization temperatures measured in calcite inclusions from the “21 de
Mayo” mine give a mean value of 233°C with a minimum of 146°C, a maximum of
360°C (Table 3) and a mode of 200°C. The salinity values range between 5.26 and
9.21 wt.% NaCl equivalent with a mean value of 7.17 and a mode of 7.5.
In calcite from the “Socavon 2001” mine (Table 4), the homogenization temperatures
measured give a mean value of 178°C with a minimum of 115°C, a maximum of 311°C
and a mode of 200°C. Salinities range between 5.71 and 23.05 wt.% NaCl equivalent
with a mean value of 18.24 and a mode of 21.0.
Fluid inclusions in barite. Only primary biphase inclusions (L+V) were measured
in the samples from two mines in question. In the Vein No. 5 (“21 de Mayo” mine)
and Vein No. 2 (“Socavon 2001” mine), the inclusions are isolated with irregular
shapes.
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Fig. 4. Distribution of salinities of fluid inclusions in gangue minerals in the “21 de Mayo” and “Socavon
2001” mines
A. Mercedes Vein — calcite; B. Anita Vein — calcite; C. Vein No. 5 — barite; D. Vein No. 2 — barite

Fig 3. Distribution of homogenization temperatures of fluid inclusions in gangue minerals in the

“21 de Mayo” and “Socavon 2001” mines
A. Mercedes Vein — calcite; B. Anita Vein — calcite; C. Vein No. 5 — barite; D. Vein No. 2 — barite
26
 TABLE 3

Data on fluid inclusions in calcite – Mercedes Vein, ”21 de Mayo” mine

Tc Te Tf Th Salinity Size
Data
[°C] [°C] [°C] [°C] [wt.% NaCl eq.] [µm]
Mean –49.43 0.73 –4.52 233.80 7.17 5.43
Standard dev. 1.89 3.42 0.80 63.58 1.13 3.20
Minimum –53.60 –33.70 –6.00 146.30 5.26 2.50
Maximum –44.60 –13.00 –3.20 360.00 9.21 12.50
Median –49.65 –20.95 –4.70 212.15 7.45 5.00
Number of measurements
24 22 24 24 24 24

TABLE 4

Data on fluid inclusions in calcite – Anita Vein, ”Socavon 2001” mine

Tc Te Tf Th Salinity Size
Data
[°C] [°C] [°C] [°C] [ wt.% NaCl eq.] [µm]
Mean –66.40 –43.32 –16.46 178.27 18.24 10.78
Standard dev. 11.01 9.85 5.42 39.86 4.90 3.82
Minimum –84.50 –53.40 –23.80 115.00 5.71 5.00
Maximum –38.00 –20.00 –3.50 311.00 23.05 20.00
Median –70.00 –47.20 –18.15 183.65 20.30 10.00
Number of measurements
28 27 28 28 23 28

TABLE 5

Data on fluid inclusions in barite – Vein No. 5, ”21 de Mayo” mine

Tc Te Tf Th Salinity Size
Data
[°C] [°C] [°C] [°C] [wt.% NaCl eq.] [µm]
Mean –64.83 –35.33 –12.10 321.33 15.84 3.75
Standard dev. 6.15 3.28 3.47 37.39 2.97 1.03
Minimum –77.00 –42.00 –19.00 258.00 13.62 2.50
Maximum –60.00 –33.50 –9.70 375.00 21.68 5.00
Median –62.65 –34.10 –10.95 322.50 14.92 3.50
Number of measurements
6 6 6 6 6 6

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 TABLE 6

Data on fluid inclusions in barite – Vein No. 2, ”Socavon 2001” mine

Tc Te Tf Th Salinity Size
Data
[°C] [°C] [°C] [°C] [wt.% NaCl eq.] [µm]

Mean –57.68 –21.00 –9.71 239.78 12.22 4.75

Standard dev. 14.29 13.17 7.87 20.10 7.64 1.19

Minimum –79.10 –38.20 –21.80 201.50 6.16 3.50

Maximum –41.30 –10.00 –3.80 263.00 23.05 6.50

Median –58.00 –11.20 –4.20 242.00 6.74 4.00

Number of measurements

7 7 7 7 7 7

The homogenization temperatures measured in the Vein No. 5 (Table 5) range

from 258 to 375°C with a mean value of 321°C. Salinities are about 15.8 wt.% NaCl
equivalent.
In Vein No. 2 (Table 6), the homogenization temperatures range from 201 to 263°C
with a mean value of 240°C. Salinities are about 12.22 wt.% NaCl equivalent.

DISCUSSION AND CONCLUSIONS

The paragenetic relations between the pyrobitumen and associated minerals in

the fractures and veins indicate that the pyrobitumen formed early in the sequence.
Textural relations between the pyrobitumen and zeolites, and the absence of graphite,
constrain the temperature range to which the pyrobitumen was subjected. The data
from fluid inclusions in barite and calcite, minerals co-genetic with the pyrobitumen,
reveal a temperature range of 180–320°C and a salinity range of 6.5–21.0 wt.% NaCl
equivalent. All these data lead to the conclusion that the mineralization took place at
moderate to low temperatures and involved fluids of considerable salinity
The organic matter exhibits relatively high reflectivity values (2.0–2.4%) that con-
firm its pyrobitumen status. Textural relations with the host rocks point out to its
hydrothermal remobilization. The d13 C values measured match the values of pe-
troleum from marine sources. The organic matter was most probably derived from the
limestone beds of the Arqueros Formation.
Paragenetic relations with the ore and gangue minerals indicate that the pyro-
bitumen was emplaced into the host rock by hydrothermal solutions that also carried
the sulphides and deposited them in the banded and brecciated veins. The pyrobitumen
occurrences in barren zones, especially in the fractures and faults that acted as channels
for post-mineralization diorite dikes, as well as in fractured dikes themselves suggest
remobilization and further migration of the organic matter.

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 Acknowledgements. This study was supported by DIULS No 020-2-10, a University de La Serena (Chile)
project and is part of a larger study of the paragenesis of the Talcuna mine district. The authors want to thank
the San Geronimo Mining Company, especially its chief geologist A. Moreno, for access to mine galleries
and for information. The kind comments and support of our colleagues, J. Oyarzun and P. Valenzuela,
are gratefully acknowledged. Special thanks are due to Prof. Dr. Andrzej Paulo for his text comments and
to Prof. Padhraig Kennan for improving the English of the text.

REFERENCES

AGUIRRE L., EGERT E., 1965: Carta Geol. Chile, No 15: Cuadrángulo Quebrada Marquesa, Provincia de
Coquimbo. Inst. Invest. Geol., 92 pp.
BORIC R., 1985: Geología y yacimientos metálicos del distrito Talcuna, IV Región de Coquimbo. Rev.
Geológica de Chile 25–26, 57–75.
CAMUS F., 1986: Yacimientos estratoligados de Cu, Pb-Zn y Ag de Chile. In: J. Frutos, R. Oyarzún,
M. Pincheira (eds), Geología y recursos minerales de Chile, 2, 547–635. University of Concepción Press,
Concepción.
CISTERNAS M.E., FRUTOS X., SPIRO B., GALINDO E., 1999: Lavas con bitumen en el Cretácico Inferior de
Copiapó, petroquímica e importancia metalogénica. Revista Geológica de Chile 26, 205–226.
DOMEYKO I., 1903: Jeolojía (Tomo V). Imprenta Cervantes, Santiago.
HUNT J. M., 1979: Petroleum geochemistry and geology. W.H. Freeman and Co., San Francisco.
MOSCOSO R., NASI C., SALINAS P., 1982: Hoja Vallenar y parte norte de La Serena, Regiones de Atacama
y Coquimbo. Serv. Nac. Geol. Miner., Carta Geol. Chile, No. 55, 100 pp.
WILSON N.S.F., ZENTILLI M., 1997: Copper sulfide formed in a degraded petroleum reservoir of the
Cretaceous Andean arc basin, Central Chile. In: J.P. Hendry et al. (eds), Geofluids II – Extended
Abstracts, 488–491.
ZENTILLI M., BORIC R., MUNIZAGA F., GRAVES M. C., 1994: Petroleum involvement in the genesis of
some stratabound copper deposits of Chile. In: Congreso Geológico Chileno No. 7, Actas, vol. 2,
1542–1546, Concepción.
ZENTILLI M., MUNIZAGA F., GRAVES M.C., BORIC R., WILSON N.S.F., MUKHOPADHAY. P.,
SNOWDON L., 1997: Hydrocarbon involvements in the genesis of ore deposits: an example in Cre-
taceous strata-bound (manto type) copper deposits of Central Chile. Intern. Geol. Review 39, 1–21.

Jimena CUCURELLA, Claudio CANUT DE BON, María Eugenia CISTERNAS

PIROBITUMINY W Z£O¯ACH SREBROWO-MIEDZIOWYCH W KREDOWEJ

SERII WULKANOKLASTYCZNEJ REJONU TALCUNA, COQUIMBO, CHILE

Streszczenie

W ostatnich latach stwierdzono obecnoœæ pirobituminów w wielu stratoidalnych z³o-

¿ach miedzi w pó³nocnej i œrodkowej czêœci Chile. W rejonie Talcuna (29°30’–29°45’ S/
/70°45’–71°00’ W) z³o¿a takie wystêpuj¹ w ska³ach dolnej kredy i zawieraj¹ 1–2% Cu,
29
0,1–0,5% Pb i 15–30 ppm Ag. Paragenezy minera³ów kruszcowych i p³onnych i mor-
fologia skupieñ pirobituminów s¹ charakterystyczne dla utworów hydrotermalnych.
Mineralizacja ta, tradycyjnie opisywana jako typu stratoidalnego (manto), wykazuje
zwi¹zek zarówno z tektonik¹ jak i litologi¹. Uskoki stanowi³y drogi przep³ywu roztwo-
rów i krystalizacji minera³ów ¿y³owych, a na ich przeciêciu z okreœlonymi horyzontami
serii wulkanoklastycznej (np. tufy lapillowe) tworzy³y siê pseudopok³adowe cia³a
rudne (manto). Pirobituminy wspó³wystêpuj¹ z minera³ami kruszcowymi (chalkopiryt,
bornit, chalkozyn), s¹ te¿ obecne w p³onnych strefach spêkañ, wype³nionych pomine-
ralizacyjnymi dajkami diorytowymi. Refleksyjnoœæ pirobituminów zmienia siê w gra-
nicach 2,0–2,4%, a analizy izotopowe wskazuj¹ na pierwotnie morskie pochodzenie
substancji organicznej (wartoœci d13C pomiêdzy –25 i –30‰). Substancja organiczna
by³a zatem mobilizowana z wapieni formacji Arqueros, prawdopodobnie przez mi-
gruj¹ce roztwory hydrotermalne, i wytr¹ca³a siê w dwóch etapach, najpierw w strefach
okruszcowanych, a póŸniej w spêkaniach dajek. Temperaturê tych roztworów okre-
œlono na 180–320°C na podstawie temperatur homogenizacji inkluzji ciek³o-gazo-
wych w kalcycie i barycie, które wspó³wystêpuj¹ z pirobituminami, a zasolenie na
6,5–21% wag. NaCl eq.