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Original Article
Shoji KOJIMA, Iván SOTO, Milenka QUIROZ, Paulina VALENCIA and Iván FERNANDEZ
1
Departamento de Ciencias Geológicas, Universidad Católica del Norte, Chile
Abstract
El Morado is the only auriferous district in the north Chilean coastal Cordillera, and has breccia-associated
Au–Fe–Cu vein-type gold deposits, such as Beatriz and Lilianita. In addition to geological and mineralogical
descriptions, geochemical characterization of the two vein deposits, and fluid inclusion and oxygen isotope
analyses of the Lilianita quartz vein were performed with the objective to elucidate their ore-forming
characteristics.
The two deposits are hosted in Late Jurassic to Early Cretaceous dioritic intrusions, and are characterized by
the oxidized mineral association of electrum (Au75Ag25 to Au85Ag15), chalcopyrite, hematite and magnetite.
Gold content of vein samples weakly correlates with Ag contents, but is not correlative with Cu contents. Fluid
inclusion data of the vein quartz indicate relatively high-trapping temperature (290 to 340°C) and low salinity
(3.2 to 13.1 wt% NaCl) conditions with low-pressure boiling evidence. The δ18O values of the corresponding
quartz samples are in a narrow range of +11.1 to +12.5 ‰. These data combined with the fluid inclusion
thermometric data suggest that the quartz-mineralizing fluid with δ18O values between +4.9 and +6.2 ‰
was derived from primary magmatic water with lesser amounts of low-temperature surface water, such as
seawater or meteoric water. All these results show that the gold deposits in the El Morado district are
intrusion-related oxidized veins, which formed from magmatic-hydrothermal fluids at relatively low-
pressure shallow conditions, compared to the Cu-rich iron oxide–copper–gold (IOCG) vein deposits in the same
province.
Keywords: El Morado district, Lilianita gold deposit, coastal Cordillera, intrusion-related oxidized vein, fluid
inclusions, oxygen isotope compositions.
Received 26 July 2016. Revised 17 October 2016. Accepted for publication 13 November 2016.
Corresponding author: S. Kojima, Departamento de Ciencias Geológicas, Universidad Católica del Norte, Av. Angamos 0610, Antofa-
gasta, Chile. Email: skojima@ucn.cl
not clearly shown which type of gold deposit the City, has small vein-type gold deposits. Since the late
Beatriz and Lilianita correspond to, nor how the gold 19th century, these deposits were exploited, and had a
deposits of the El Morado district were generated in maximum 75 g/t Au and an average grade of 20 g/t
the coastal Cordillera. This study presents geologic Au in their prosperous period (Boric et al., 1984, 1990).
and geochemical features of the Beatriz and Lilianita After the Second World War the gold deposits were
gold deposits, particularly in relation to the chemical developed intermittently, but are closed now.
data of the two gold–quartz veins, as well as fluid The El Morado district is mainly composed of
inclusion and oxygen isotope data of the Lilianita thick Jurassic andesite strata (termed the La Negra
gold–quartz vein, to elucidate metallogenic characteris- Formation), Late Jurassic to Early Cretaceous gra-
tics of the El Morado gold district and to estimate the nitic intrusions, Cretaceous conglomeratic sediments
origin of the Lilianita vein-forming ore fluid. (termed the Caleta Coloso Formation) and Cenozoic
alluvial covers (Fig. 1). The La Negra Formation
consists mainly of monoclinal andesitic to basaltic
2. Outline of geology and the deposits andesite lavas with lesser amounts of tuff breccias,
sandstone and limestone (García, 1967; Boric et al.,
The eastern part towards the Mejillones Peninsula in 1990; Kojima et al., 2003). The Late Jurassic to Early
northern Chile is composed of the three districts, Cretaceous granitic intrusions are plutonic complexes
Naguayán, El Desesperado and El Morado (Fig. 1), of holocrystalline gabbroic to granitic units of the
where more than 30 small copper mines are known magnetite-series and calc-alkaline suite (Ishihara et al.,
(Boric et al., 1990). These mines have generally high- 1984; Fernandez, 2004). The Cerro Fortuna intrusion
grade copper averages up to 4 wt% Cu, and have been body covering the El Morado district is variable in com-
exploited since the 1850s (Arce, 1930). Among these, position, comprising of diorite and tonalite to granodi-
only the district El Morado (23°16.5´S, 70°21´W), which orite units (González, 1996). The hornblende–biotite
is located approximately 40 km north of Antofagasta diorite to quartz diorite unit as the host rock was dated
Fig. 1 Simplified geologic map around the El Morado district of the coastal Cordillera in Antofagasta Region (from Boric
et al., 1990; Ordenes, 2002).
Lilianita samples (Nos. ML-02, 03, 05, 06, 07, 08, 09) of 4. Analytical results
the main-stage crystalline quartz, which have primary
fluid inclusions of sufficient sizes for measurements.
4.1 Geochemistry of quartz veins and electrum
Furthermore, six quartz specimens except ML-08 were Chemical compositions of the vein specimens are
also provided for oxygen isotope analysis. Crystalline summarized in Table 1. The Au contents of the ana-
and pure portions of these quartz specimens were lyzed samples are generally below the lower limit of
carefully separated, and finely powdered in an agate detection, however several samples report detectable
mortar. Au, with the maximum concentration of 17.6 ppm
(C11) and 2.7 ppm (A6) from the Beatriz and Lilianita
specimens, respectively (Table 1). In these Au-rich
3.2 Analytical methods samples the correlating Ag contents yield 0.6 ppm
and 7.4 ppm in the two samples, respectively, and the
Major element (Al, Fe, Mg, Ca, Na, K, Ti, and P), and 32 Ag content is weakly correlated with Au contents of
minor and trace element (Ag, As, Au, Ba, Be, Bi, Ce, the Beatriz and Lilianita veins. However no positive
Cd, Co, Cr, Cu, Hf, La, Li, Mn, Mo, Nb, Ni, Pb, S, Sb, correlation between the Au and Cu contents is contras-
Sc, Sn, Sr, Ta, Th, U, V, W, Y, Zn, and Zr) analyses of tively displayed in the analyzed samples. In the
principal vein-bands in the Beatriz and Lilianita gold Au-detectable samples of the Lilianita vein (A4 to A6)
deposits (21 samples) were made using an inductively the Au and Cu contents exhibit a negative correlation.
coupled plasma-mass spectrometer (ICP-MS) at ACME Noticeably, the Cu contents are high in the two veins,
Analytical Laboratories (Vancouver, Canada). Each ranging up to 5.57 wt% at Beatriz, but with a low Au
sample was treated for 1 hour in HCl–HNO3–HF– value of 0.1 ppm. At the Beatriz vein the contents of
HClO4 solution for each 0.5 g sample. The composition Au, Ag, Cu, Pb and Zn at the upper zone (BU samples
of electrum grains in the Lilianita samples was semi- in Table 1) are generally higher than those of the
quantitatively verified using an Oxford Inca EDS lower zone (BL samples in Table 1). The Fe-rich sam-
system (Oxford, Concord, MA, USA) combined with ples with abundant hematite are generally enriched in
a JEOL JSM6360LV-type scanning electron microscope elements as Mn, Co, As, V and W. It is known that
(SEM; JEOL, Akishima, Japan) at the Universidad these elements are all detected in hematite as a prin-
Católica del Norte (UCN), Chile. cipal mineral from iron oxide–copper–gold (IOCG)
The thermal analyses of primary inclusions in quartz deposits (Carew, 2004). As suggested earlier, the quartz
were carried out to obtain their homogenization veins contain host rock residue as rutile. Thus the
temperature (Th) and salinity values, using a Linkam high contents of such rock-forming elements as Na, K
THMSG600-type heating-freezing stage equipped with and Ca may be considered as a result of host rock
TMS 93-LNP programmable controllers (Linkam assimilation.
Scientific Instruments, Surrey, UK) at UCN, Chile. The SEM-EDS examination of three Lilianita samples
All samples were prepared as doubly polished thin represents normalized chemical compositions of elec-
sections approximately 0.3 mm thick. Heating rates trum in a range of Au75Ag25 to Au85Ag15. No other
of 1 to 2°C/min and 0.1 to 0.6°C/min were adopted Au- or Ag-bearing minerals except for electrum were
for the Th and ice melting temperature measurement, observed in all the samples. Thus the electrum com-
respectively. The salinity equivalent to NaCl wt% positions are conformable with the aforementioned
was obtained using the equation involving a de- feature that the Au content is weakly correlated with
gree of freezing point depression (see Table 1 in Ag contents in the Au-detectable samples.
Bodnar, 1993).
Oxygen was extracted from 5 mg samples at 550–
600°C according to the conventional BrF5 procedure 4.2 Microthermometry and oxygen isotope
of Clayton and Maeda (1963). Isotope compositions compositions
were analyzed on Themo-Finnigan Delta plus XP
Continuous-Flow Isotope-Ratio Mass Spectrometer Primary fluid inclusions in transparent quartz of the
(CF-IRMS) at Queen’s University, Canada. All δ18O main-stage which coexists with Au–Cu minerals, were
values are given in units of permil (‰) relative examined including the viewpoints of necking and
to VSMOW international standard, with a precision leaking range. All inclusions examined are of two-
of ±0.1 ‰. phase liquid–vapor (L–V) and vapor–liquid (V–L)
Al wt% 9.44 9.43 9.37 9.49 5.54 11.07 7.56 8.75 8.87 8.71 8.05 1.23 0.51 3.54 9.41 8.06 7.86 8.27 8.40 6.82 2.25
Fe wt% 5.71 5.66 5.43 5.93 23.70 4.51 6.71 5.18 5.60 5.45 2.79 10.71 0.96 5.15 1.81 1.77 1.81 2.52 3.40 7.15 9.89
Mg wt% 2.33 2.26 2.20 1.06 0.30 0.62 1.71 2.10 2.14 2.08 2.57 0.15 0.32 1.72 1.96 2.49 3.28 2.54 1.83 1.33 0.44
Ca wt% 5.08 5.07 5.00 1.56 0.19 1.81 0.42 5.88 4.77 4.77 7.27 0.11 34.97 8.79 8.39 7.57 9.01 7.88 1.50 1.33 1.92
Na wt% 2.68 2.82 2.65 2.49 0.18 2.15 0.12 2.37 2.65 2.55 4.38 0.12 0.06 0.10 4.92 4.85 4.11 3.91 0.30 0.46 0.59
K wt% 1.25 0.94 1.27 1.88 2.21 1.65 2.79 1.12 1.24 1.30 0.18 0.29 0.08 0.61 0.21 0.14 0.21 0.21 3.06 2.17 0.12
Ti wt% 0.533 0.454 0.459 0.551 0.158 0.380 0.296 0.354 0.546 0.494 0.734 0.034 0.031 0.111 0.893 0.648 0.695 0.727 0.331 0.439 0.010
P wt% 0.091 0.080 0.093 0.033 0.094 0.030 0.071 0.055 0.091 0.083 0.083 0.015 0.015 0.026 0.165 0.139 0.164 0.107 0.135 0.049 0.013
Abbreviations: LL, Lilianita; BL, Lower zone of Beatriz (331 m high); BU, Upper zone of Beatriz (355 m high)
201
El Morado vein-type gold deposits
S. Kojima et al.
5. Discussion and remarks Table 2 δ18O values of the Lilianita quartz samples and
those of mineralizing fluid calculated
5.1 Origin of ore fluid
Sample Av. Th Th range (No. δ18Oquartz δ18Ofluid
The Lilianita primary fluid inclusions show evidence of no. (°C) of inclusions) (‰) (‰)
boiling, and thus the Th values obtained can be regarded ML-02 342 314–362 (9) 11.7 6.2
as the mineralizing temperatures. Accordingly, the δ18O ML-03 315 234–367 (16) 12.5 6.2
values of mineralizing fluids were calculated using ML-05 321 286–350 (8) 11.7 5.6
the fractionation factor (α) of oxygen isotope between ML-06 320 297–367 (14) 11.6 5.4
ML-07 294 202–352 (21) 12.2 5.1
quartz and water (Matsuhisa et al., 1979): ML-09 321 270–358 (15) 11.1 4.9
1000 ln α = 3.34(106/T2) – 3.31,
Fig. 3 Photomicrographs of (A) liquid-rich two-phase inclusions and (B) coexistence of liquid-rich and vapor-rich inclusions
from the Lilianita deposit. The scale bars are 20 μm.
and the average Th values of the corresponding (2) The “amount effect” of rainfall is not considered
quartz specimens. According to the experimental here, because there is no information on Late Jurassic
results of Horita and Wesolowski (1994), the oxygen to Early Cretaceous climates of northern Chile.
fractionation between water and vapor is very minute Thus, the δ18O variation due to the amount effect is
in high-temperature hydrothermal conditions. Thus, assumed to be included in the estimated δ18O range
the boiling effect in the oxygen isotope fractionation of meteoric water.
was not considered here. (3) The oxygen isotope ratios of meteoric water
As stated earlier, some gaseous inclusions exhibit can be inferred from the Miocene Precordillera data
vapor/liquid immiscibility during inclusion capturing. (δ18O = 5.5 to 7.5 ‰, Agemar et al., 1999) and the
Some of these inclusions have Th values higher than present precipitation data of northern Chile
about 370°C (Fig. 4), which are not indicative of real (δ18O = 3.5 to 9.0 ‰, Squeo et al., 2006; Herrera &
Th data. Thus, all the Th values higher than 370°C were Custodio, 2014).
excluded in calculating the average Th values. The δ18O On the basis of these assumptions, it can be esti-
values of mineralizing fluids are listed in Table 2, which mated at a probable range of δ18O = 4 to –8 ‰ for
suggests that the δ18O values of mineralizing fluid the Late Jurassic to Early Cretaceous meteoric water.
(+4.9 to +6.2 ‰) overlap the lower range relative to Meanwhile the δ18O composition of oceanic seawa-
the common δ18O range of +6.0 to +10 ‰ for primary ter during geologic history is a subject of controversy.
magmatic water (e.g., Cambell & Larson, 1998; Hoefs, Muelenbachs (1998) insisted that the δ18O composition
2009). Figure 5 shows a correlative relation between of the oceanic seawater is buffered to a constant δ18O
the δ18O and Th values of the mineralizing fluids, values near 0 ‰ (VSMOW) by hydrothermal and
suggesting slight dilution of a low-temperature and weathering processes at mid-oceanic ridges. However,
low-δ18O surface water with deep-seated magmatic Wallmann (2001) modeled a strong 18O-depletion in
water. Indeed, we can obtain δ18Owater ≈ 0.0 ‰ at seawater in Paleozoic ages. Even if the Wallmann’s
T = 25°C, using the least squared equation of δ18Owater model is adopted for the δ18O composition of seawater,
(‰) = 0.019 T (°C) –0.52 (Fig. 5). only <0.5 ‰ depletion is generated in Late Jurassic to
The oxygen isotope composition of meteoric water in Early Cretaceous seawater. Thus the δ18O composition
Late Jurassic to Early Cretaceous ages, when the gold of seawater in the mineralization ages could be
deposits of the El Morado district were formed, has approximated to ~0 ‰.
not yet been defined. Nonetheless, we can estimate The δ18O ranges of all the fluid reservoirs in discus-
the probable δ18O range under the following sion, which were possibly related to the El Morado
assumptions: gold mineralization, are summarized in Figure 6. The
(1) The altitude and latitude, which highly affect δ18O oxygen isotopic range of the mineralizing fluids is
composition of meteoric water, were not significantly explained by mixing of magmatic water with the
different in the mineralization age (Late Jurassic to seawater or meteoric water. Such a fluid mixing may
Early Cretaceous) to the present period. have played an important role in the Au deposition.
several principal types based on their geochemical The Th and salinity data also support an alternative
associations. The Au-vein deposits of Mesozoic coastal idea that gold deposits in the El Morado are shallow
provinces in Northern Chile, which were generated in manifestations of the Cu-rich IOCG-type deposits.
association with highly oxidized calc-alkaline intru- The high-temperature and hypersaline fluids related
sions emplaced at Cordilleran margins above active to the formation of the IOCG would have been highly
subduction zones, are characterized by Au–Fe oxide– diluted by low-temperature and low-salinity surface
Cu association. Pluton-related vein-type gold deposits water to produce the El Morado mineralizing fluid.
similar to the El Morado Au deposits occur in the However, such a large-scale mixing is not deduced
Mantos de Punitaqui (30°50´S, 70°15´W) of the from the present oxygen isotope data of the vein
Coquimbo district. These deposits also comprise Au, quartz. It is therefore suggested that the El Morado
Fe oxides and Cu minerals characterized as Early gold mineralization is initially distinct from the Cu-rich
Cretaceous “intrusion-related oxidized vein” deposits IOCG mineralization in terms of fluid source.
(Sillitoe, 1991; Sillitoe & Thompson, 1998). Thus, the A similar Au–Fe oxides–Cu vein-type deposit
Mantos de Punitaqui and also Cu-rich IOCG vein named India Coya (27°36´S, 70°23´W), which is hosted
deposits in the coastal Cordillera of the Antofagasta in a Cretaceous granodioritic intrusion of the Copiapó
region are comparable to the El Morado gold deposits district, has been recently exploited (Osorio et al.,
in their mineralization characteristics. 2015; Cortés, 2016). Unfortunately, no fluid inclusion
Primary fluid inclusions in the Lilianita quartz-vein and isotope data have yet been presented for the
deposit exhibit a boiling phenomenon, which is vein deposit, and so further geochemical studies
inferred to have occurred at 290 to 340°C. Applying including fluid inclusion research are required for
the measured salinities at the temperature range to the deposit to compare with gold deposits in the
the experimental results of Bischoff and Pitzer (1989), El Morado.
a fairly low-fluid pressure of less than about 140 bars
(~14 MPa) could be estimated for the gold–quartz
mineralization. It is known that a low-pressure boiling 6. Conclusions
system prefers Au to partition to the brine phase in the
case of saline fluids (Simon et al., 2005). Polyphase 1. Only the El Morado district has quartz vein-type
saline inclusions coexisting with vapor-rich inclusions gold deposits (Beatriz, Lilianita) in the north Chilean
are reported in the Mantos de Punitaqui gold mineral- coastal Cordillera, which are hosted in a Late Jurassic
ization (Sillitoe & Thompson, 1998), and thus it is likely dioritic intrusion of the magnetite-series and calc-
that a low-pressure boiling was a significant trigger for alkaline suite.
formation of the gold-partitioned saline fluids. The 2. Gold and silver mineralization of the deposits is
mineralizing fluid responsible for the Lilianita ore characterized by the occurrence of electrum (Au75Ag25
formation is not associated with saline phases, and so to Au85Ag15). Other ore minerals include chalcopyrite,
it is not certain whether the low-pressure boiling could specular hematite and magnetite, suggesting the
be an effective factor for the Au concentration. By intrusion-related oxidized vein-type deposit deno-
contrast, the Cu-rich IOCG deposits of the same region minated by Sillitoe and Thompson (1998).
have high-salinity polyphase (39–68 wt% NaCl) and 3. The analyzed Au contents of the veins weakly
high Th (401–560°C) fluid inclusions in quartz veins, correlate with Ag contents, but are not correlative with
and the boiling phenomenon is not observed (Tristá & Cu contents.
Kojima, 2003). In general, high-temperature hypersa- 4. Fluid inclusion data exhibit a relatively high-
line solution enhances chloride complexing in copper temperature (290 to 340°C) and low salinity (3.2 to
transport under magmatic-hydrothermal conditions 13.1 wt% NaCl) ranges at fairly low-pressure (< ~
(e.g., Liu & McPhail, 2005). This phenomenon suggests 140 bars) boiling conditions.
a great Cu-transport capacity of the high-Th hypersa- 5. The δ18O values of quartz-vein samples from the
line fluids related to the Cu-rich IOCG deposits. Lilianita deposit are in a narrow range of +11.1 to
Currently, the main trigger of the Au concentration of +12.5 ‰. Combining these data with the Th data, the
gold deposits in the El Morado still remains uncertain, δ18O values of the mineralizing fluids are estimated
but it can probably be implied that the P–T–X to be between +4.9 and +6.2 ‰. The δ18O range implies
condition is an important factor for the formation of that the mineralizing fluid originated from primary
Au-enriched magmatic-hydrothermal solutions. magmatic water with a small amount of low-
temperature surface water, such as seawater or Cortés, J., Marquardt, C., González, G., Wilke, H.G. and
meteoric water. Marinovic, N. (2007) Cartas Mejillones y Peninsula de
Mejillones, Región de Antofagasta. Serv. Nacional Geol.
6. The estimated fluid δ18O data of the Lilianita de- Minería, Carta Geol. Chile Nos. 103 and 104, Santiago, 58p.
posit exclude the idea that the El Morado gold deposits Espinoza, S., Véliz, H., Esquivel, J., Arrias, J. and Moraga, A.
are shallow manifestations of the Cu-rich IOCG-type (1996) The cupriferous province of the coastal range, northern
deposits in the same region. Chile. In Camus, F., Sillitoe, R. H., Petersen, R. (eds.) Andean
copper deposits: New discoveries, mineralization, styles and
metallogeny, Soc. Econ. Geol. Spec. Publ., no. 5, Society of Eco-
nomic Geologists, Inc., Littleton, 19–32.
Acknowledgments Fernandez, I. (2004) Aspectos petrográficos de los intrusivos
jurásicos-cretácicos asociados a procesos de mineralización
aurífera, entre las Quebradas Mejillones y el Desesperado,
Part of the expenses of this study was covered by the
Cordillera de la costa, Segunda Región de Chile. Graduate
vice-rectory of Universidad Católica del Norte, to Thesis, Univ. Católica del Norte, Antofagasta, 124p.
which we express our sincere thanks. We would like García, F. (1967) Geología del Norte Grande de Chile. Symp. sobre
to thank Dr. Andrew Menzies who improved this el geosinclinal andino. Soc. Geol. Chile, Santiago, No. 3, 138p.
manuscript, and Drs. Y. Watanabe, Y. Morishita and González, G. (1996) Evolución tectónica de la Cordillera de la
Costa de Antofagasta (Chile): Con especial referencia a las
R. Takahashi for their critical reading of the manuscript.
deformaciones sinmagmaticas del Jurasico-Cretacico Inferior.
Thanks are due to Leonel Jofre of Universidad Católica Berl. Geowiss. Abh., Reihe A, 181, 1–111.
del Norte who completed the original figures used in Herrera, C. and Custodio, E. (2014) Origin of waters from small
this article. springs located at the northern coast of Chile, in the vicinity
of Antofagasta. Andean Geol., 41, 314–341.
Hoefs, J. (2009) Stable isotope geochemistry, 6th edn. Springer-
Verlag, Berlin, Heidelberg, 285.
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