Ma.I. Hermo et al.

Ore Geology Reviews 143 (2022) 104724

Fig. 13. Representative fluid inclusions in the different QBX facies of the Didipio deposit. (a) Liquid-rich liquid–vapor (LV) inclusion from QBX-Act. (b) Slightly
irregular-shaped fluid inclusions from QBX-Act. (c) Brine-type fluid inclusion from QBX-Act. (d) Vapor-rich fluid inclusion coexisting in the same assemblage as an
LVS-type from Qtz-Act. (e) Liquid-rich LV inclusions from QBX-Un, enclosed in a yellow dotted box is the inset map of the next figure. (f) Zoomed in photo of the LV-
type fluid inclusion. (g) Brine-type fluid inclusion, obtained from QBX-Un, which homogenizes by halite dissolution. (h) Fluid inclusion from QBX-Un that ho­
mogenizes by vapor disappearance. (i) Vapor-rich fluid inclusion from QBX-Un. Abbreviations: L – liquid, V – vapor, S – solid. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)

but in the former, Pb-Se occurs as clausthalite (PbSe), while in the latter,
it occurs as Se-bearing galena (PbS). The deposition of selenide minerals
typically occurs at relatively higher ƒO2 conditions, where selenium is
geochemically separated from S-Se complex in the hydrothermal fluids
and there is a smaller amount of sulfide species dissolved (Takahashi
et al., 2007; Škácha et al., 2017).
In stage 4, gold occurs as invisible gold in early-forming pyrite and as
native gold intergrown with lower temperature mineral assemblages.
Early in stage 4, the temperature must have been high enough such that
the gold entered solid solutions due to its high solubility (Tomkins and
Mavrogenes, 2001). Later in the paragenesis, either the gold was
scavenged by vapor or leached by later solutions as suggested by the
occurrence of barren anhedral pyrite crystals (Kesler et al., 2002). Since
native gold almost always coexisted with tellurides and Bi-sulfosalts, it is
likely that Au-Ag-Te-Se-Bi rich fluid occurred in solid solution with
early-forming sulfides and exsolved during cooling (<320 ◦ C) as sepa­
rate phases. This temperature estimate is derived from the fluid inclu­
sion data associated with the stage 4 mineralization where native gold
was found.

16
Ma.I. Hermo et al. Ore Geology Reviews 143 (2022) 104724

Table 6
Summary of the microthermometric data of the fluid inclusions from each breccia facies. All fluid inclusions are secondary. Legend: FIA = fluid inclusion assemblage; L
= liquid; V = vapor; Sn = solid with n number present.
Facies Sample FIA n Phases Volume of vapor Tm(◦ C) Salinity (wt.% NaCl Th(◦ C) Homogenization
present (%) equivalent) mode

QBX- DDDH083 A 3 LV 30 − 5.7 to − 4.5 7.2 to 8.8 304 to 309 Vapor disappearance
Act 414.59 B 1 LVS 10 51.6 437 Halite dissolution
C 1 LVS2 20 49.7 420 Halite dissolution
E 4 LV 30–50 − 2.3 to − 1.8 3.0 to 3.9 430 to 470 Vapor disappearance
RDUG030 129.1 A 2 LVS 10–30 49.8 to > 57.8 420 to > Halite dissolution
500
QBX-Un DDDH250 A 4 LVS2 20–30 48.8 to 49.8 410 to 417 Halite dissolution
176.81 B 3 LVS3 20 50.3 to 50.8 427 to 434 Vapor disappearance
DDDH250 A 18 LV 40–50 − 26.3 to 22.1–26.4 427 – 450 Vapor disappearance
177.85 − 19.6

Fig. 14. Histograms showing (a) homogenization temperature and (b) NaCl
equivalent for fluid inclusions from QBX-Act and QBX-Un. Fluid inclusions
(observed in QBX-Act) that did not homogenize within the limit of 500 ◦ C of the
Linkam stage are recorded as > 500 ◦ C.
6. Conclusions
Combined microscopic work and geochemical techniques used on
the quartz-fragment-rich breccia (QBX) suggest that the deposit is
comprised of several paragenetic facies with unique clast and matrix
compositions and varying gold concentration due to a late-stage inter­
mediate sulfidation mineralization event overprinting the earlier-
formed porphyry-style mineralization. Brecciation events between
Fig. 15. Hydrothermal model of the QBX deposit. Base model adapted from
Blackwell (2017).
substages lead to the variation in cement mineral assemblages. The re­
sults of this study helped to constrain the conditions of ore formation in
the QBX as summarized in more detail below.
Most of the porphyry-style mineralization formed in the distal and
lower contact facies which generally have low gold grade. As com­
plemented by fluid inclusion data, the mineral assemblage of chalco­
pyrite, bornite, biotite, and magnetite indicates a high formation
temperature (420–440 ◦ C) and a magmatic source for the hydrothermal
fluids. This high temperature may have been the result of vapor phase
entrapment from the boiling fluids.

17
Ma.I. Hermo et al.
Fig. 16. Plot of salinity vs. homogenization temperature. Marker shape refers
to QBX facies while color of symbols refers to fluid inclusion type. Each point
represents an FIA. NaCl saturation curve is obtained from Potter et al., (1977)
while the H2O-NaCl critical curve is obtained from Atkinson (2002). Brine-type
fluid inclusions are above the NaCl curve and LV-type fluid inclusions are
below it.
As the hydrothermal system cooled down, the moderate-high grade
central facies and upper contact facies were cemented by lower-
temperature (300–320 ◦ C) ore assemblage of calcite, base-metal sul­
fides, tellurides, selenides, and Bi-sulfosalt supported by low salinity
fluid inclusion data (3–4 wt% NaCl equiv.) characteristic of epithermal-
style mineralization. Occurrence of selenides indicates a relatively
higher ƒO2 condition for Se to effectively separate from S during mineral
deposition.
The gold in the QBX deposit has three main occurrences: (1) Au-Ag-
Cu-Te blebs (gold telluride) (2) native gold, and (3) invisible gold. The
gold telluride is associated with the porphyry-style mineralization and
occurs as blebs along the boundaries of bornite-chalcopyrite sym­
plectites believed to have been exsolved from the high-temperature
sulfides during cooling. The native gold and invisible gold are associ­
ated with the epithermal-style mineralization. Native gold is intergrown
with an assemblage of silver tellurides, Bi-sulfosalts, selenides, and base-
metal sulfides implying a lower temperature of environment
(300–320 ◦ C). Dissolved gold is contained within stage 4 early-formed
pyrite associated with the native gold-bearing samples.
The intimate relationship between gold (either in form of native
element and/or as gold-silver tellurides) and other trace minerals that
incorporate Bi, Te, and Se in their structure corroborates the Ag-Bi-Te
scavenger model. It suggests that a magmatic hydrothermal ore-
forming fluid with Bi, Se, and Te scavenged the Au at high tempera­
tures; the gold occurs in solid solution with the sulfides (i.e., early-
forming pyrite with invisible gold) and then subsequently exsolved or
crystallized at lower temperatures.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
We would like to express our appreciation to the Mine Geology and
18
Ore Geology Reviews 143 (2022) 104724
Exploration staff of Oceana Gold Philippines, Inc. and to Oceana Gold
Corporation for permitting us to conduct the study and for providing
logistical support. We also like to extend our deepest gratitude to the
Graduate School of International Resource Sciences, Dr. Sofia Frias, Dr.
Pearlyn Manalo-Balmater, and Dr. James Refran of Akita University for
assisting in sample preparation and SEM-EDS, EPMA, and fluid inclusion
microthermometry analyses. This work was supported by the JSPS
Grant-in-Aid for Scientific Research (17K06982), the Japan Mining
Promotive Foundation, and the Society of Resource Geology. In addi­
tion, this project was also partially funded by the Continuous Opera­
tional and Outcomes-based Partnership for Excellence in Research and
Academic Training Enhancement (COOPERATE) which is administered
by the Office of International Linkages, University of the Philippines.
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