©2021 Society of Economic Geologists, Inc.

Economic Geology, v. 116, no. 6, pp. 1267–1284

Evolution of the Magmatic-Hydrothermal System at the Santa Rita

Porphyry Cu Deposit, New Mexico, USA: Importance of Intermediate-Density
Fluids in Ore Formation
Subaru Tsuruoka,1,†,* Thomas Monecke,1 and T. James Reynolds1,2
1Center for Mineral Resources Science, Department of Geology and Geological Engineering, Colorado School of Mines,
1516 Illinois Street, Golden, Colorado 80401, USA
2FLUID INC., 1401 Wewatta Street #PH3, Denver, Colorado 80202, USA

Abstract
The Santa Rita porphyry Cu deposit in New Mexico, USA, is characterized by a stockwork of three vein types
that differ in morphology, mineralogy, and associated alteration assemblages. Early quartz veins associated
with potassic alteration are composed of recrystallized granular quartz grains that host ubiquitous hypersa-
line liquid and vapor-rich fluid inclusions. The early quartz likely formed at high (≳500°C) temperatures and
lithostatic pressures. Hypogene Cu mineralization at Santa Rita is in sulfide veins that reopened or crosscut
the early quartz veins. The sulfide veins are surrounded by alteration halos containing chlorite and K-feldspar.
Rare quartz crystals are present in some of these chalcopyrite and pyrite veins. The cores of the quartz crystals
contain hypersaline liquid and vapor-rich fluid inclusions, whereas the rims mostly contain hypersaline liquid
inclusions. The quartz crystals are interpreted to have formed close to the ductile-brittle transition as a result
of the pressure drop from lithostatic to hydrostatic conditions. Formation of the quartz crystals was postdated
by the deposition of Cu sulfides. Grain boundaries between the quartz and the sulfide minerals are irregular
in shape, with sulfide crosscutting growth zones in the quartz. The Cu sulfides are interpreted to have formed
from intermediate-density fluids that form secondary fluid inclusion assemblages in all earlier-formed quartz
types. Microthermometric investigations showed that these fluid inclusion assemblages homogenize at ~385°
to 435°C by critical or near-critical behavior and have salinities of <10 wt % NaCl equiv. The precipitation of
Cu sulfides occurred as a result of cooling of these fluids following their escape from the lithostatic into the
hydrostatic realm. Retrograde quartz solubility caused the corrosion of earlier-formed quartz during Cu sulfide
deposition. The youngest veins at Santa Rita are composed of quartz and pyrite. These veins are associated with
intense sericite alteration that overprinted all earlier alteration assemblages. The late quartz hosts primary and
secondary liquid-rich fluid inclusions, but no intermediate-density fluid inclusions were identified. This quartz
vein type formed at temperatures <360°C and hydrostatic pressures. The paragenetic relationships show that
hypogene Cu mineralization at Santa Rita postdated potassic alteration of the host rocks. The Cu mineralization
was formed by cooling intermediate-density fluids with critical or near-critical densities as they escaped from
lithostatic to hydrostatic conditions.
Introduction eralization (Nash and Theodore, 1971; Eastoe, 1978; Ulrich
Porphyry copper deposits are the world’s most important et al., 1999; Rusk et al., 2008; Maydagán et al., 2015; Gregory,
source of copper, with precious metals commonly being re- 2017), although some workers have suggested that low-salin-
covered as by-products. Hypogene ores in these deposits ity vapors may also be involved in Cu transport (Heinrich,
constitute large, low-grade stockwork and disseminated sul- 2005; Williams-Jones and Heinrich, 2005; Klemm et al., 2007;
fide zones that are spatially associated with porphyritic intru- Pudack et al., 2009; Mernagh et al., 2020). In some depos-
sions forming apophyses to larger stocks that have been em- its, however, zones of high Cu grades can be correlated with
placed within the upper (≤1–10 km) part of the crust (Nielsen, the occurrence of abundant veins lacking quartz but consist-
1968; Lowell and Guilbert, 1970; Gustafson and Hunt, 1975; ing almost entirely of Cu sulfides (Pollard and Taylor, 2002;
Seedorff et al., 2005; Sillitoe, 2010). Sapiie and Closs, 2013; Stefanova et al., 2014; Braxton et al.,
Mineralization in porphyry Cu deposits is widely regarded 2018; Sun et al., 2020). These veins, ranging in thickness up
to have formed early in the evolution of these magmatic- to several millimeters, crosscut the early quartz veins associ-
hydrothermal systems. Early quartz veins commonly contain ated with potassic alteration and in many cases appear to be
chalcopyrite or bornite, and the associated potassic-altered associated with chlorite-rich alteration. The lack of quartz in
host rocks may contain abundant disseminated sulfides. In these veins suggests that sulfide precipitation occurred at con-
addition, a broad spatial overlap between Cu contours and ditions of retrograde quartz solubility (Redmond et al., 2004;
the distribution of the potassic alteration is common in many Landtwing et al., 2010; Stefanova et al., 2014; Monecke et al.,
deposits. Based on fluid inclusion studies on the early quartz 2018, 2019; Sun et al., 2020), which is inconsistent with hy-
veins, many workers have concluded that hypersaline liquids persaline liquids being responsible for the formation of these
responsible for the potassic alteration also cause the Cu min- veins (Landtwing et al., 2010; Monecke et al., 2018, 2019).
This study reexamines the previous observations constrain-
†Corresponding author: e-mail, subaru.tsuruoka@icrag-centre.org
ing the relative timing and the nature of the mineralizing
*Present address: Irish Centre for Research in Applied Geosciences, School magmatic-hydrothermal fluids at the Santa Rita porphyry Cu
of Earth Sciences, University College Dublin, Belfield, Dublin 4, Ireland. deposit in New Mexico, USA (Leroy, 1954; Nielsen, 1968; Ja-
ISSN 0361-0128; doi:10.5382/econgeo.4831; 18 p.
Digital appendices are available in the online Supplements section. 1267 Submitted: February 10, 2020 / Accepted: December 25, 2020

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by Raymond Rivera Cornejo
 1268 TSURUOKA ET AL.

cobs and Parry, 1979; Ahmad and Rose, 1980; Parry et al.,
1984; Reynolds and Beane, 1985). Nielsen (1968) showed that
ore at Santa Rita is confined to thin sulfide veins crosscutting
the earliest quartz veins. Chlorite and K-feldspar are pres-
ent in the alteration halos associated with these sulfide veins,
overprinting the earlier potassic alteration (Reynolds and
Beane, 1985). Previous fluid inclusion investigations on Santa
Rita focused on the early, high-temperature quartz stockwork
veins associated with potassic alteration that formed prior
to the ore and on the later quartz associated with phyllic al-
teration that postdates mineralization, because the Cu sul-
fide veins do not contain macroscopically identifiable quartz
(Ahmad and Rose, 1980; Reynolds and Beane, 1985). In the
current study, a combination of microanalytical techniques
including optical cathodoluminescence (CL) microscopy and
trace element analysis of quartz by electron microprobe was
employed to better constrain the quartz paragenesis at Santa
Rita, as well as the textural relationships between the quartz
and sulfide minerals in the veins. The new observations sug-
gest that neither the hypersaline liquids and vapors commonly
associated with potassic alteration nor the liquids responsible
for the phyllic alteration formed the ore. It is proposed that
Cu sulfides at Santa Rita were deposited from a single-phase,
magmatic-hydrothermal fluid of critical or near-critical den-
sity.
Geologic Setting
The Santa Rita porphyry deposit is located in southwest New
Mexico and currently exploited by the Chino open-pit opera-
tion. It is one of ~50 porphyry deposits that constitute the
American Southwest porphyry metallogenic belt. The por-
phyry deposits are aligned along a northwest to southeast
trend and are associated with felsic calc-alkalic intrusions that
were emplaced into Precambrian basement and Paleozoic-
Mesozoic sedimentary rocks during the Laramide orogeny
(~70–55 Ma) as a result of plate subduction along an Andean-
type continental margin (Titley, 1993).
The Precambrian basement rocks in the Santa Rita area
consist of crystalline gneiss, micaceous schists, greenstone,
and quartzite. The basement rocks are covered by a ~1.2-km-
thick succession of relatively undeformed sedimentary rocks.
This includes Cambrian to Permian quartzite, limestone, do-
lostone, and shale, which are unconformably overlain by Cre-
taceous sandstone and shale (Fig. 1; Hemon et al., 1953; Rose
and Baltosser, 1966; Jones et al., 1967).
Igneous activity at Santa Rita commenced in the Late Cre-
taceous with the intrusion of quartz diorite porphyry form-
ing sills and laccoliths (Fig. 1; Kerr et al., 1950; Jones et al.,
1967). The Santa Rita granodiorite stock was emplaced in the
Paleogene (~55 Ma; Hannink, 2010). Skarn is well-developed
around the contact between the intrusions and Cambrian
limestone. Postmineralization igneous activity resulted in the
emplacement of several dike generations (i.e., quartz mon-
zonite, quartz monzonite porphyry, latite, and quartz latite)
that cut across the Santa Rita granodiorite stock and into the
surrounding sedimentary host rocks (Fig. 1; Kerr et al., 1950;
Hemon et al., 1953; Rose and Baltosser, 1966; Jones et al.,
1967).
Stockwork veins are developed in and around the Santa
Rita granodiorite stock (Nielsen, 1968). The earliest vein type,
referred to as A veins using the nomenclature of Gustafson
and Hunt (1975), consists of gray quartz (Fig. 2a). The A veins
lack internal symmetry or open vugs. They range in morphol-
ogy from irregular and wavy to planar (Leroy, 1954; Nielsen,

Fig. 1. Geologic map of the Santa Rita porphyry Cu deposit, New Mexico. Geology from Rose and Baltosser (1966) and Jones
et al. (1967). Geology of the Santa Rita granodiorite stock and distribution of potassic alteration from Nielsen (1968). Location
of Whim Hill breccia from Reynolds and Beane (1985). The pit outline reflects the current stage of mining. The Whim Hill
breccia has been mined out entirely. Map on left of figure shows the location of the study area.

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by Raymond Rivera Cornejo
 SANTA RITA PORPHYRY Cu DEPOSIT, NEW MEXICO 1269

Fig. 2. Hand specimen photographs of the different vein types recognized at Santa Rita as well as a representative sample of
the Whim Hill breccia. a. Stockwork of A veins. The veins are associated with hydrothermal K-feldspar and biotite. Quartz in
the A veins is referred to as QA. Sample RSR6. b. Narrow C vein consisting of pyrite and chalcopyrite. The vein is surrounded
by a narrow alteration halo containing chlorite. Igneous biotite is altered to chlorite. Sample RSR5-2a. c. Narrow C vein
hosted by altered granodiorite. The alteration halo surrounding the vein consists of chlorite and hydrothermal K-feldspar.
Igneous biotite and earlier-formed hydrothermal biotite are altered to chlorite. Sample RSR10. d. Stockwork of different
vein types illustrating crosscutting relationships. A narrow, irregularly shaped A vein consisting of gray quartz is the earliest
vein type in the sample. The A vein is crosscut by C veins that have different orientations and range from fractures coated by
pyrite and chalcopyrite to narrow veins that are up to ~1 mm in thickness. Late D veins consisting of pyrite and minor quartz
crosscut both earlier vein types. The granodiorite hosting the veins has been affected by pervasive sericite alteration. The
presence of chalcopyrite in the C veins was confirmed petrographically. Sample 25148. e. Late D vein formed by reopening
of an earlier A vein. The white quartz is referred to as QD. The vein is surrounded by sericite-altered granodiorite. Sample
25134. f. Euhedral quartz crystals in the Whim Hill breccia. The cores of large quartz crystals have different inclusion char-
acteristics from the rims and are referred to as QBL. The outer parts of the crystals, as well as the smaller euhedral quartz
crystals, are composed of quartz referred to as QD. In addition to quartz, small euhedral pyrite crystals are present in open
spaces. Sample RSR15. Bt = hydrothermal biotite, Chl = chlorite, Chl. Bt = chloritized igneous biotite, Cpy = chalcopyrite,
Ksp = hydrothermal K-feldspar, Py = pyrite, Ser = sericite.

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by Raymond Rivera Cornejo
 1270
1968). They are associated with alteration halos in which ig-
neous biotite and hornblende phenocrysts are replaced by
pale-brown hydrothermal secondary biotite. Hydrothermal
K-feldspar replaced igneous plagioclase and pervaded the
groundmass (Nielsen, 1968; Jacobs and Parry, 1979).
Thin veins composed of chalcopyrite and pyrite crosscut the
early A veins (Fig. 2b-d; Nielsen, 1968). These are referred to
as C veins following the nomenclature of Dilles and Einaudi
(1992) and Gustafson and Quiroga (1995). In most cases, these
veins are less than a few millimeters in width and macroscopi-
cally resemble planar hairline fractures coated with sulfides
as opposed to classic stockwork veins (Fig. 2c). When broken
open, the sulfide minerals occur as coating on fracture surfac-
es. The C veins are the carrier of hypogene copper mineral-
ization at Santa Rita (Nielsen, 1968). Although Nielsen (1968)
reported the alteration around these veins to be typified by
green biotite, Reynolds and Beane (1985) demonstrated that
the alteration selvages surrounding the veins are dominated
by chlorite and minor K-feldspar (Fig. 2b, c). Both igneous
biotite phenocrysts and hydrothermal biotite are commonly
replaced by pale-green chlorite along vein selvages.
Both earlier vein types are reopened or crosscut and off-
set by late veins consisting of quartz, pyrite, and sericite (Fig.
2d, e), referred to as D veins according to the nomenclature
of Gustafson and Hunt (1975). The D veins are the young-
est vein type at Santa Rita and most abundant at the margin
of the Santa Rita granodiorite stock. They are typically up to
several centimeters thick and occur as continuous linear veins
that are associated with extensive sericite alteration halos that
overprint all earlier alteration mineral assemblages (Leroy,
1954; Nielsen, 1968; Parry et al., 1984; Reynolds and Beane,
1985).
Several breccia pipes have been exposed within the San-
ta Rita granodiorite stock during the mining operation. The
Whim Hill breccia was the largest breccia body (500 × 100 m)
located in the northern part of the granodiorite stock (Fig. 1).
The breccia consisted of angular fragments of granodiorite,
with rock flour forming the breccia matrix. Euhedral quartz,
K-feldspar, apatite, chlorite, and pyrite cemented open space
within the breccia (Fig. 2f; Kerr et al., 1950; Reynolds and
Beane, 1985).
Materials and Methods
This study is based on samples originally collected from the
open pit of the Santa Rita porphyry deposit for the research
conducted by Reynolds and Beane (1985). Details on sam-
ple locations are given by Reynolds and Beane (1985). The
samples represent all three porphyry vein types recognized
at Santa Rita and include samples from the Whim Hill brec-
cia. Emphasis was placed on reinvestigating samples of the
C veins as these are the main host to mineralization. Doubly
polished 80-µm-thick sections were prepared from the vein
samples. In addition, thick sections previously prepared for
the study by Reynolds and Beane (1985) were examined.
The vein mineralogy, fluid inclusion petrography, and the
composition of the alteration halos associated with the veins
were studied in transmitted and reflected light using an Olym-
pus BX51 optical microscope. Classification of fluid inclusion
types followed Monecke et al. (2018). Micron-scale textural
relationships were investigated with a TESCAN MIRA3
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by Raymond Rivera Cornejo
TSURUOKA ET AL.
LMH Schottky field emission-scanning electron microscope
(FE-SEM) equipped with a single-crystal YAG backscat-
tered electron (BSE) detector. Imaging was conducted at a
working distance of 10 mm and an accelerating voltage of
15 kV. Semiquantitative chemical analyses of minerals were
performed by energy-dispersive X-ray spectroscopy (EDS)
using an attached Bruker XFlash 6/30 silicon drift detector.
Quartz veins and samples from the Whim Hill breccia were
also investigated by optical CL microscopy. A HC5-LM hot
cathode CL microscope by Lumic Special Microscopes, Ger-
many, was used and operated at 14 kV and a current density of
~10 µA mm–2 (Neuser, 1995). CL images were captured with
a high-sensitivity, double-stage Peltier cooled Kappa DX40C
CCD camera. Acquisition times of CL images of quartz ranged
from 8 to 10 s. In addition to the study of the fluid inclusion
inventory of vein quartz, it was attempted to study pyrite in
the C veins using a DAGE-MTI LSC-70 2,200-nm infrared
camera attached to the optical microscope. However, no trans-
parent pyrite suitable for fluid inclusion studies was present.
The distributions of Al, K, and Ti in quartz showing differ-
ent CL responses were determined by electron microprobe
analysis using a JEOL JXA-8900 at the U.S. Geological Sur-
vey in Denver. Trace element mapping was conducted at an
accelerating voltage of 20 kV and a beam current of 100 nA
(measured on the Faraday cup). A focused electron beam was
used, with dwell times of 1 s/pixel. The trace element maps
for the three elements were collected simultaneously, with
one spectrometer and a TAP analyzing crystal being used to
measure Al, one spectrometer and a PET analyzing crystal
measuring K, and the three remaining spectrometers detect-
ing Ti using LiF analyzing crystals. In addition to mapping,
spot analyses were conducted along traverses across selected
quartz crystals. Spots along the traverses were chosen careful-
ly to avoid surface pits and mineral inclusions. The operating
conditions for spot analyses included an accelerating voltage
of 20 kV, a beam current of 50 nA (measured on Faraday cup),
and a beam defocused to 10 μm to minimize specimen dam-
age. The analysis of Al, K, and Ti was performed using the dis-
tribution of spectrometers and analyzing crystals mentioned
above. Count times of 10 min on the peak and 5 min on each
high and low background were applied. Alternating on- and
off-peak acquisition was employed to account for carbon con-
tamination buildup during the long analysis times. Aggregate
intensities of the on- and off-peak positions of the duplicate
elements and a blank correction were used to improve the
counting statistics (Donovan et al., 2011). Calculated detec-
tion limits on spot analyses are 8 ppm for Al, 15 ppm for K,
and 13 ppm for Ti. The results of the electron microprobe
analyses are given in Appendix 1.
Limited microthermometry was performed on intermedi-
ate-density fluid inclusions in quartz grains that were also
studied by the analytical methods described above. Fol-
lowing the procedures outlined in Goldstein and Reynolds
(1994), microthermometric investigations were performed
on assemblages of inclusions with a FLUID INC.-adapted
U.S. Geological Survey gas-flow heating and freezing stage
following calibration using synthetic fluid inclusions at
–56.6°, 0.0°, and 374.0°C. Final apparent ice-melting tem-
peratures were determined by bracketing to 0.1°C using
the cycling technique described by Goldstein and Reynolds
 SANTA RITA PORPHYRY Cu DEPOSIT, NEW MEXICO
(1994). Measurement was not always possible, because the
inclusions were too small or because clathrate crystals were
present during cycling. Cycling could not be employed for
precise homogenization temperature determinations, as the
phase boundary separating liquid and vapor forms within a
few degrees or less with cooling after homogenization. Fi-
nal homogenization was, therefore, approximated within a
temperature interval of 5°C. The microthermometric data
obtained are reported in Table 1.
Results
A veins
The A veins at Santa Rita are associated with potassic altera-
tion characterized by the occurrence of secondary K-feldspar
and biotite in the altered wall rocks. The veins consist of anhe-
dral quartz grains, referred to here as QA (Fig. 3). The quartz
grains exhibit undulose extinction, and adjacent grains typi-
cally have different extinction angles. Growth banding is rare
in the QA grains (Fig. 3a, b). The granular nature of the quartz
and the rare occurrence of primary growth banding suggest
that quartz has undergone extensive recrystallization.
QA is characterized by a bright, short-lived, light-blue CL
emission. During continued electron bombardment, the
short-lived blue CL transitions to a long-lived royal-blue or
indigo emission. Growth banding visible in plane-polarized
light can be recognized based on subtle color variations (Fig.
3c). Locally, the QA is crosscut by a second type of quartz that
has a dark-purple CL (Fig. 3c).
Electron microprobe spot analyses revealed that QA in the
A veins contains 87 to 1,309 ppm Al, with a median value
of 120 ppm Al. The concentrations of K vary from <15 to
793 ppm. The quartz has a median K value of 28 ppm. The
measured Ti concentrations range from 21 to 199 ppm, with
a median of 55 ppm (App. 1; Fig. 4). The concentrations of
all three elements are typically higher in quartz exhibiting the
royal-blue CL emission than quartz of indigo CL color.
QA contains abundant fluid inclusions, some of which ex-
hibit textural evidence for postentrapment modification (Fig.
3d-g) but many of which do not (Fig. 3h). The abundance
of fluid inclusions is typically so high that individual planes
of secondary fluid inclusions cannot be readily identified. In-
clusion types identified in the A veins at Santa Rita include
hypersaline liquid inclusions, vapor-rich fluid inclusions, in-
termediate-density fluid inclusions, and liquid-rich fluid in-
clusions (Fig. 3h).
C veins
The A veins at Santa Rita are crosscut by C veins. These veins
are thin (<5 mm) with planar walls and commonly contain
dark-green chlorite within the fractures and in alteration sel-
vages with K-feldspar, where chlorite replaced igneous and
earlier-formed hydrothermal biotite. In most cases, the C
veins do not contain quartz. In rare instances where minor
quartz is present in the C veins, it is not optically distinct from
QA and was not recognized as a separate quartz type in previ-
ous studies. However, because of the distinct textural setting,
this quartz is referred to here as QB. The rare quartz forms
anhedral to euhedral grains that are ~200 to 500 mm in their
longest dimension (Fig. 5). The quartz crystals occur along
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by Raymond Rivera Cornejo
1271
Table 1. Microthermometric Data Obtained on Intermediate-Density
Fluid Inclusions from Santa Rita Showing Critical or Near-Critical
Homogenization Behavior
Homogeniza- Number of Temperature Salinity
tion tempera- inclusions in of last ice (wt % Evidence for
ture (°C) assemblage melting (°C) NaCl equiv) clathrate
Sample RSR15a
385–390 3 – – –
390–395 2 –1.1 1.9 No
400–405 1 –7.2 10.7 Yes
410–415 2 – – –
430–435 3 –3.0 5.0 No
Sample RSR11b
395–400 1 – – –
400–405 1 – – –
Note: – = not observed
the vein walls or are entirely enclosed by the sulfide minerals.
Contacts between the quartz crystals and sulfide minerals are
typically scalloped and irregular (Fig. 5a, b).
The QB crystals show differences in optical CL properties
from core to rim, which broadly correlate with variations in
trace element concentrations observed along electron mi-
croprobe traverses. Based on the combination of optical CL
microscopy and electron microprobe investigations, two dif-
ferent subtypes of QB can be distinguished (App. 1; Figs. 4,
5). The earliest type of quartz, referred to as QBE, is character-
ized by a dark-purple or dark-red CL emission. The QBE has
high Al concentrations ranging from 63 to 3,414 ppm, with a
median value of 208 ppm. Many of the analytical spots have
K concentrations below the detection limits of 15 ppm. The
maximum K value measured is 999 ppm and the median value
is 96 ppm. The Ti concentrations range from <13 to 86 ppm,
with a median value of 30 ppm (App. 1; Fig. 4). The dark-red
QBE is characterized by higher Al contents when compared
to the dark-purple QBE (App. 1; Fig. 5c, d). The dark-red and
dark-purple QBE form complex interlocking textures. In some
cases, isolated islands of dark-purple QBE are surrounded by
dark-red QBE (Fig. 5b). Elsewhere, both types of quartz oc-
cur as growth bands within larger quartz crystals (Fig. 5c).
The later QB subtype, referred to as QBL, is characterized by a
maroon CL emission. The quartz forms an overgrowth on QBE
(Fig. 5a-c). Zones of QBL have low trace element concentra-
tions. The Al concentrations range from 23 to 366 ppm, with
a median value of 87 ppm. The K and Ti contents of QBL are
generally below detection (App. 1; Fig. 4).
Grains of QBE typically host abundant secondary hypersa-
line liquid inclusions (Fig. 5e), vapor-rich fluid inclusions, and
rare intermediate-density fluid inclusions (Fig. 5f). Obvious
visual evidence for postentrapment modification of the fluid
inclusions is typically absent, but small variations in the liquid
to vapor volumetric proportions indicate that some hypersa-
line liquid inclusions could have been affected by postentrap-
ment modification. Vapor bubbles and halite daughter crystals
in hypersaline liquid inclusions in QBE are smaller than many
found in QA. In contrast to QBE, the QBL is largely devoid of
fluid inclusions and appears distinctly clear under the opti-
cal microscope. Hypersaline liquid inclusions are present, but
vapor-rich inclusions are exceedingly rare. Reconnaissance
heating experiments show that the hypersaline liquid inclu-
 1272 TSURUOKA ET AL.

Fig. 3. Photomicrographs, optical cathodoluminescence (CL) images, and fluid inclusion inventory of QA forming A veins at
Santa Rita. a. Plane-polarized light image of QA. The quartz grains are anhedral with irregular grain boundaries. The arrow
highlights the location of faint growth zones in one of the large quartz grains. b. Crossed-polarized light image of the same field
of view as in Figure 3a. The quartz grains have different orientations. The arrows highlight contacts between polygonal grains
forming triple junctions that have interfacial angles of ~120°, providing strong evidence for recrystallization. The quartz shows
first-order colors, as the sample is a thick section. c. Optical CL image of the quartz grain in Figure 3a and b showing relict
growth banding. The quartz exhibits a stable royal-blue to indigo luminescence. The growth bands are locally crosscut by dark-
purple quartz (arrows) interpreted to be QBE. The locations of microprobe spot analyses are given and are keyed to Appendix
1. d. High-magnification image of QA containing abundant decrepitated fluid inclusions, some of which are highlighted by the
arrows. e. Image of a hypersaline liquid inclusion in QA showing irregular surfaces (arrow), interpreted to have been caused by
postentrapment modification. f. Fluid inclusion that has been affected by postentrapment modification. g. Intermediate-den-
sity fluid inclusion with surfaces that suggest postentrapment modification. h. Fluid inclusion inventory in QA. Hypersaline liq-
uid inclusions, vapor-rich fluid inclusions, and liquid-rich fluid inclusions are ubiquitous in QA, as is reported for many porphyry
deposits worldwide (Monecke et al., 2018). In addition, intermediate-density inclusions can be found but easily mistaken for
vapor-rich fluid inclusions. Note that intermediate-density fluid inclusions not affected by postentrapment modification show
negative crystal shapes. The hypersaline liquid inclusions contain halite and commonly other daughter phases including sylvite,
anhydrite, magnetite, and hematite (cf. fig. 6 in Reynolds and Beane, 1985). Small triangular opaque crystals interpreted to be
chalcopyrite can be seen in some of the hypersaline liquid inclusions. Due to the high abundance of intersecting microfrac-
tures, individual planes of secondary fluid inclusions are difficult to discern. All images are from sample RSR6. HS = hypersa-
line liquid inclusion, ID = intermediate-density fluid inclusion, L = liquid-rich fluid inclusion, V = vapor-rich fluid inclusion.

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by Raymond Rivera Cornejo
 SANTA RITA PORPHYRY Cu DEPOSIT, NEW MEXICO 1273

Fig. 4. Histogram plots of Al, K, and Ti concentrations in the different types of quartz occurring at the Santa Rita porphyry
Cu deposit. Trace element analyses were performed by electron microprobe. DL = detection limit.

sions typically homogenize by halite disappearance after the
vapor. Grains of QBL are also crosscut by trails of secondary
intermediate-density fluid inclusions (Fig. 5f, g), which may
contain a tiny opaque daughter mineral (Fig. 5g).
Many intermediate-density fluid inclusions in QB have neg-
ative crystal shapes and contain large vapor bubbles (Fig. 5f,
g). Only a few fluid inclusion assemblages could be identi-
fied that are of sufficient size to allow confident microther-
mometric investigations (Table 1). The inclusions in these
assemblages showed critical or near-critical homogenization
behavior (cf. Klyukin et al., 2019) at ~385° to 435°C. Some
intermediate-density fluid inclusions exhibited a double jerk
on cooling, and ice could not be obtained by cycling, suggest-
ing the presence of a clathrate compound. For the inclusions
where final ice-melting temperatures could be determined,
the apparent salinities are <10 wt % NaCl equiv (Table 1).
D veins
The D veins at Santa Rita consist of quartz and pyrite.
These veins have straight walls and are commonly associ-
ated with intense sericitic alteration halos that pervasively
overprint earlier-formed hydrothermal minerals. Quartz in
the D veins is referred to here as QD. It forms large sub-
hedral to euhedral grains that exhibit a CL emission that
ranges from dark to light red brown (Fig. 6a-d). The trace
element concentrations of QD are generally low. The con-

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Fig. 5. Photomicrographs, optical cathodoluminescence (CL) images, and fluid inclusion characteristics of QB crystals in chal-
copyrite-pyrite veins at Santa Rita. a. Plane-polarized light image of quartz crystals occurring along the wall of a chalcopyrite-
pyrite vein. The quartz consists of early QBE characterized by the presence of hypersaline liquid and vapor-rich fluid inclusions
(not shown). A distinct overgrowth of later QBL can be recognized by the paucity of fluid inclusions. The quartz exhibits scal-
loped grain boundaries in contact with chalcopyrite. Sample RSR15a. b. Optical CL image of the same field of view as shown in
Figure 5a. The QBE is characterized by a dark-purple or dark-red emission. The later overgrowth of QBL exhibits a maroon CL.
The locations of microprobe spot analyses are given and keyed to Appendix 1. c. Optical CL image of a quartz crystal enclosed
by chalcopyrite. Most of the crystal consists of QBE showing a dark-purple or dark-red emission. A small clear overgrowth of
QBL with maroon CL occurs along the upper right and lower left sides of the crystal. The chalcopyrite crosscuts the contact
between QBE and QBL. The locations of microprobe spot analyses are given and keyed to Appendix 1. Sample RSR15a. d. Elec-
tron microprobe map of the same crystal showing the distribution of Al in the quartz crystal (dark blue = low concentrations,
light blue = elevated concentrations). The dark-red optical CL emission of QBE coincides with elevated Al contents. The appar-
ent differences in grain shape between the optical CL image and the electron microprobe map are a result of the experimental
setup. The optical CL images are collected looking through the back of the thin section during electron bombardment of the
polished surface. e. Hypersaline liquid inclusions occurring in QBE. The small inclusions form a secondary assemblage that
does not appear to have been affected by postentrapment modification. Sample RSR15a. f. Large, secondary, intermediate-
density fluid inclusions hosted by QBE. The inclusions homogenize by critical behavior at ~400° to 405°C. Sample RSR15a.
g. Intermediate-density fluid inclusions containing an opaque daughter crystal (arrows). The inclusions do not appear to have
been affected by textural modification after their entrapment. Sample RSR12. Cpy = chalcopyrite.

centrations of Al range from 85 to 1,186 ppm, with a median
value of 220 ppm. The K and Ti contents of QD is typically
below detection limit (App. 1; Fig. 4). In general, the optical
CL properties and trace element characteristics of QD are
similar to those of QBL.
Grains of QD contain rare primary and abundant secondary
liquid-rich fluid inclusions (Fig. 6e). No intermediate-density
fluid inclusions are present in QD. Except for necking, tex-
tures suggestive of postentrapment modification are absent,
and liquid to vapor volumetric proportions within individual
fluid inclusion assemblages are usually consistent. Homogeni-
zation temperatures and salinities of the liquid-rich fluid in-
clusions were previously determined to range from ~260° to
360°C, with maximum salinities of up to ~9 wt % NaCl equiv
(Reynolds and Beane, 1985).
Whim Hill breccia
The Whim Hill breccia consists of abundant wall-rock frag-
ments set in a matrix of rock flour. Open spaces contain large
(up to 3 cm) euhedral quartz crystals (Figs. 2f, 7a-e). The rock
fragments are commonly potassic altered and host earlier A
veins. Chlorite is present along growth zones in the quartz
crystals (Fig. 7a, b) or as a coating on top of the quartz crystals
with pyrite, suggesting that chlorite formed synchronous with

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Fig. 6. Photomicrographs, optical cathodoluminescence (CL) images, and fluid inclusion characteristics of QD in late D veins
at Santa Rita. a. Large quartz grain of QD that is surrounded by pyrite. b. Optical CL image of the same field of view as in Fig-
ure 6a illustrating that QD exhibits a red-brown emission. Subtle growth zoning can be recognized in the quartz. The locations
of microprobe spot analyses are given and keyed to Appendix 1. c. Euhedral quartz grain grown into open space, forming a
vuggy centerline in the same quartz-pyrite vein. d. Optical CL image of the same field of view as in Figure 6c. The QD growth
zones are characterized by red-brown and dark red-brown emissions. e. Quartz in the D veins contains only liquid-rich fluid
inclusions, some of which are highlighted by the arrows. The shapes of the secondary fluid inclusions in the various assem-
blages vary from negative crystal shaped to irregularly shaped, correlating with the observation that a wide range of homog-
enization temperatures (~250°–350°C) was determined (Reynolds and Beane, 1985) for the different primary and secondary
fluid inclusion assemblages in this sample. No evidence of postentrapment modification of fluid inclusions is present in QD,
except that the irregular shapes of many inclusions are a result of necking. All images are from sample RSR6a. Py = pyrite.

the late growth zones of the coarse euhedral quartz crystals
and also after deposition of most of the quartz.
Crystals cut perpendicular to the c axis show growth bands
(Fig. 7a) defined by variations in CL intensity and color. The
cores of large euhedral quartz crystals exhibit a maroon CL
(Fig. 7b), locally with dark-purple growth bands, which is simi-
lar to the signature of QBL. Trace element analyses of the quartz
indicate that Al concentrations vary from 50 to 1,084 ppm,
with a median value of 138 ppm. The K content ranges from
<15 to 663 ppm K, while Ti analyses returned values largely
below the detection limits. Only a few analytical spots yielded
values of up to 1,100 ppm Al and 700 ppm K (App. 1; Fig. 4).
Late growth zones of the quartz crystals have a dark to
light red-brown CL emission (Fig. 7b, d), which resembles
the signature of QD in D veins. Well-developed oscillatory
growth zoning can be observed. Trace element maps ob-
tained by electron microprobe analyses revealed that the Al
concentrations vary between individual growth bands visible
in CL (Fig. 7e), whereas the Ti concentrations are uniformly
low. Electron microprobe analyses of QD contained in the
Whim Hill breccia yielded values of 24 to 2,586 ppm Al, with
a median value of 288 ppm. The K and Ti concentrations are
typically below the limit of detection although values as high
as 308 ppm K and 47 ppm Ti have been registered (App. 1;
Fig. 4).
The cores of the large quartz crystals of the Whim Hill
breccia are characterized by the presence of rare hypersa-
line liquid inclusions (Fig. 7f). Vapor-rich fluid inclusions are
exceedingly rare. In contrast, the late growth zones contain
only liquid-rich fluid inclusions, many of which define growth
bands (Fig. 7g). Homogenization temperatures and salini-
ties of these primary liquid-rich fluid inclusions are similar to
those recorded for QD (Reynolds and Beane, 1985).
Discussion
The research presented here confirms key findings of previ-
ous paragenetic studies at Santa Rita (Nielsen, 1968; Reyn-
olds and Beane, 1985). However, application of a combination

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 1276 TSURUOKA ET AL.

Fig. 7. Photomicrographs, optical cathodoluminescence (CL) images, and fluid inclusion characteristics of quartz crystals
from the Whim Hill breccia at Santa Rita. a. Crossed-polarized light image of a quartz crystal from the Whim Hill breccia cut
approximately perpendicular to the c axis. The core of the crystal consists of QBL and the outer portion of the crystal is com-
posed of QD. Individual growth zones highlighted by the arrows are defined by primary liquid-rich fluid inclusions. Chlorite
occurs in the growth zones formed after QBL. Sample RSR5. b. Optical CL image of the same field of view as in Figure 7a.
Both quartz types are characterized by growth zoning and are difficult to distinguish based on their emission color. The loca-
tions of microprobe spot analyses are given and keyed to Appendix 1. c. Plane-polarized light image of a quartz crystal from
the Whim Hill breccia cut parallel to the c axis. The part of the crystal shown consists of QD hosting liquid-rich fluid inclusions
only. Sample RSR5-2b. d. Optical CL image of the same field of view as in Figure 7c. The crystal exhibits a red-brown to dark
red-brown CL emission and is characterized by well-developed oscillatory and sector zoning. The locations of microprobe
spot analyses are given and keyed to Appendix 1. e. Electron microprobe map of the same field of view as in Figure 7c, d
showing the distribution of Al in the quartz crystal. The subtle variations in emission color coincide with variations in Al
concentration (dark blue = low concentrations, red = high concentrations). f. Small hypersaline liquid inclusions (highlighted
by arrows) hosted by QBL of the Whim Hill breccia. Sample RSR5-2b. g. Growth zone defined by primary, liquid-rich fluid
inclusions within a late overgrowth of QD. The growth zone is crosscut by a secondary assemblage of liquid-rich fluid inclu-
sions. Sample RSR5. Chl = chlorite.

of microanalytical techniques, including optical CL micros-
copy and electron microprobe analysis, allowed distinction
of quartz types not previously identified. The fluid inclusion
petrographic characteristics of these quartz types provide new
insights into the evolution of the magmatic-hydrothermal sys-
tem at Santa Rita and the processes responsible for Cu miner-
alization at this deposit.
Paragenetic sequence and distinction of quartz types
The results of this study highlight that the reconstruction of
paragenetic relationships in porphyry veins is challenging, as
repeated reopening of the veins during the evolution of the
magmatic-hydrothermal systems results in complex over-
printing relationships at the microscale (Penniston-Dorland,
2001; Rusk and Reed, 2002; Pudack et al., 2009; Müller et
al., 2010; Landtwing et al., 2010; Stefanova et al., 2014; Sun
et al., 2020). At Santa Rita, identification of different quartz
types had to rely on a combination of analytical methods, in-
cluding optical microscopy, fluid inclusion petrography, CL
investigations, and electron microprobe analysis. The use of
any single analytical method would not have been successful.
For instance, QA and QBE have similar fluid inclusion inven-
tories and display only subtle differences in their CL charac-
teristics. However, the trace element concentrations in both
quartz types are distinct. On the other hand, the quartz types
QBL and QD can be readily distinguished based on their fluid
inclusion inventory, as the QD quartz contains no hypersaline
liquid inclusions. However, the optical CL emission and trace
element concentrations in both quartz types are similar (Fig.
8). In addition, the abundances of Al, K, and Ti vary signifi-

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 SANTA RITA PORPHYRY Cu DEPOSIT, NEW MEXICO 1277

Fig. 8. Summary diagram illustrating the characteristics of the different vein and quartz types recognized at Santa Rita. CL
= cathodoluminescence.

cantly within a given quartz type, and adjacent growth zones
of the same quartz type can show large compositional differ-
ences. This suggests that the incorporation of trace elements
into the quartz was controlled by nonequilibrium processes.
Early quartz vein formation
The A veins associated with potassic alteration represent the
earliest vein type at Santa Rita. The irregular and wavy shape
of some A veins, which includes crenulated and ptygmatically
folded veins (Nielsen, 1968), suggests that early vein forma-
tion occurred in a host rock that exhibited plastic behavior
(Gustafson and Hunt, 1975; Brathwaite et al., 2001; Sillitoe,
2010). Temperatures of formation of the veins may have been
≳500°C as suggested by the potassic alteration around the
veins (Jacobs and Parry, 1979) and isotopic evidence (Shep-
pard et al., 1971).
The formation of the A veins followed the emplacement of
the Santa Rita stock at ~55 Ma (Hannink, 2010). Magmatic-
hydrothermal fluids derived from the magma chamber were
rising through the already solidified part of the porphyritic in-
trusion, forming the early quartz veins at high temperatures.
Fluid inclusion petrography shows that hypersaline liquid
and vapor-rich fluid inclusions predominate in QA (Ahmad and
Rose, 1980; Reynolds and Beane, 1985; this study), suggest-
ing that A vein formation took place at conditions correspond-
ing to those of the two-phase field of the H2O-NaCl system
(Fig. 9a; Bodnar, 1995). However, conditions must have also
intersected the single-phase field, as intermediate-density in-
clusions are also present (Fig. 9a). Because of the high tem-
peratures of the cooling but already solidified intrusion, fluid
flow through the granodiorite must have occurred at ductile
conditions, precluding open fracture development except
during short periods of high strain (cf. Fournier, 1991, 1998).
Numerical simulations by Weis et al. (2012) showed that fluid
flow through ductile rocks self-organizes into overpressure-
permeability waves. Within the upward-moving waves, pres-
sures exceed lithostatic conditions, resulting in the creation of
permeability. Behind the wave, pressure drops to lithostatic
conditions, resulting in quartz precipitation and sealing of the
permeability. Over the lifetime of a magmatic-hydrothermal
system, many of these waves pass through the porphyry, creat-
ing a stockwork of veins.

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 1278 TSURUOKA ET AL.

Fig. 9. Pressure-temperature diagrams illustrating the conditions at which different vein types encountered at Santa Rita are
likely to have formed. The diagrams show the phase relationships in the H2O-NaCl model system at a salinity of 5 wt % NaCl
equiv. Overlain in a, c, and d are quartz solubility isopleths in millimoles SiO2 per kilogram water. a. The QA in the A veins con-
tains abundant hypersaline liquid and vapor inclusions suggesting that the early quartz formed at high temperatures within the
two-phase field of the H2O-NaCl system. Intermediate-density inclusions are also present and were entrapped at somewhat
lower temperatures within the single-phase field. The orange field outlines the lithostatic pressure conditions and temperature
range at which the early veins are inferred to have formed. Cooling and decompression of the magmatic-hydrothermal fluids
during fluid ascent from a magma chamber causes a decrease in quartz solubility, resulting in quartz vein formation. The room
temperature petrographic characteristics of fluid inclusions entrapped in the quartz are shown schematically. The irregular
shape of the fluid inclusions entrapped at lithostatic conditions results from postentrapment modification of the inclusions that
occured during later decompression from lithostatic to hydrostatic conditions. b. The QB present in reopened A veins and in
some C veins formed as the magmatic-hydrothermal system transitioned from lithostatic to hydrostatic conditions close to the
ductile to brittle boundary. The inferred temperature and pressure conditions of quartz formation are outlined by the blue
field. The early QBE containing hypersaline liquid and vapor-rich inclusions formed within the two-phase field of the H2O-NaCl
system. The later QBL contains hypersaline liquid inclusions but only exceedingly rare vapor-rich inclusions, suggesting that this
quartz type formed as a result of cooling of the hypersaline liquid at conditions that allowed physical segregation and escape
of the buoyant vapor phase. The fluid inclusions in both quartz types have been trapped at hydrostatic conditions, as evidence
for postentrapment textural modification is largely absent. c. The C veins are interpreted to have formed from intermediate-
density fluids that have critical to near-critical densities. Cooling of these fluids would have resulted in the precipitation of
sulfides under conditions of retrograde quartz solubility. The temperature and pressure conditions are schematically outlined
by the blue field. As no quartz precipitated from these fluids, intermediate-density fluid inclusions can only be observed as
secondary assemblages in earlier formed quartz. d. The late QD in the D veins formed as a result of cooling of magmatic-
hydrothermal liquids at hydrostatic conditions. The blue field schematically indicates the inferred conditions of QD formation.
The QD contains primary and secondary liquid-rich fluid inclusions. Phase relationships from Driesner and Heinrich (2007).
Quartz solubility isopleths and granodiorite solidus from Monecke et al. (2018). Quartz solubility isopleths in the two-phase
region represent the total quartz solubility in the liquid and coexisting vapor. CP = critical point, GD solidus = H2O-saturated
granodiorite solidus, F = single-phase fluid, H = halite, L = liquid, V = vapor.

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 SANTA RITA PORPHYRY Cu DEPOSIT, NEW MEXICO
The petrographic characteristics of QA in the A veins at
Santa Rita suggest that the quartz has undergone extensive
recrystallization. Most notable are the vitreous nature of the
quartz in hand specimen and the granular appearance of the
quartz under the microscope. The widespread occurrence of
polygonal grains forming triple junctions that have interfacial
angles of ~120° provides strong evidence for grain-scale re-
crystallization. The recrystallized QA at Santa Rita is charac-
terized by a homogeneous CL emission, and remnant grains
showing growth zoning are only locally preserved (Fig. 3a,
b). Recrystallization of QA must have occurred during the
early evolution of the magmatic-hydrothermal system when
the Santa Rita granodiorite hosting the veins was still ductile.
Repeated reopening and sealing of the early porphyry veins
during the passage of the overpressure-permeability waves
modeled by Weis et al. (2012) may have resulted in recrystal-
lization of earlier-formed quartz and the precipitation of new
quartz that is recrystallized during a subsequent fluid flow
event. This process of recrystallization appears to be a fun-
damental process in porphyry deposits, as quartz in A veins
of porphyry deposits worldwide shows similar petrographic
characteristics (Gustafson and Hunt, 1975; Hedenquist et al.,
1998; Landtwing et al., 2010; Stefanova et al., 2014; Monecke
et al., 2018; Acosta et al., 2020). This contrasts with quartz in
later vein types formed subsequent to a decline in tempera-
ture and the concomitant shift from ductile to brittle behavior
of the host rocks. Quartz in the late veins is commonly euhe-
dral to subhedral (Gustafson and Hunt, 1975; Hedenquist et
al., 1998; Monecke et al., 2018).
The QA in the A veins at Santa Rita contains fluid inclu-
sions that were entrapped during the passage of the overpres-
sure-permeability waves and the subsequent evolution of the
magmatic-hydrothermal system. Many of the fluid inclusions,
including hypersaline liquid and vapor-rich inclusions as well
as inclusions of intermediate density, show textural evidence
for postentrapment modification (Fig. 3d-g). Experimental
investigations suggest that these textural modifications are a
result of pronounced changes in pressure (Sterner and Bod-
nar, 1989), which presumably occurred after the formation
of the A veins as the magmatic-hydrothermal system cooled
and transitioned from lithostatic to hydrostatic pressures (cf.
Gustafson and Hunt, 1975; Monecke et al., 2018; Sun et al.,
2020). Postentrapment modification makes these fluid inclu-
sion assemblages unsuitable for the measurement of homog-
enization temperatures and perhaps salinities (Sterner and
Bodnar, 1989; Chang et al., 2018; Sun et al., 2020). In con-
trast, ubiquitous secondary fluid inclusions trapped in QA late
in the evolution of the magmatic-hydrothermal system at hy-
drostatic conditions do not show evidence for postentrapment
modification. These fluid inclusion assemblages have consis-
tent liquid to vapor volumetric proportions and yield reliable
homogenization temperatures (Reynolds and Beane, 1985)
but are not related to QA formation (Sun et al., 2020).
Lithostatic-hydrostatic transition
Some of the C veins at Santa Rita contain rare QB crystals that
occur along the vein walls or are entirely enveloped by the
sulfide minerals. The QB is younger than the QA, as C veins
crosscut A veins. This second generation of quartz at Santa
Rita was not previously recognized by Reynolds and Beane
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1279
(1985), because it is rare and indistinguishable from QA with a
standard petrographic microscope.
The QB at Santa Rita is interpreted to be equivalent to the
quartz present in B veins in other porphyry Cu deposits (Mo-
necke et al., 2018). Similar to Santa Rita, this type of quartz
commonly occurs in reopened A veins (Redmond et al., 2004;
Müller et al., 2010; Bennett et al., 2014; Skewes, 2016; Sun
et al., 2020). For instance, Redmond et al. (2004) reported
that porphyry veins at Bingham Canyon in Utah contain early
quartz, interpreted to be equivalent to QA of this study, that
occurs as interlocking anhedral grains. The quartz has a mod-
erate to bright luminescence and shows irregular zoning in
panchromatic CL images. The second quartz generation, in-
terpreted to be QB of this study, occurs along fractures and
shows well-developed oscillatory growth zoning. Similar ob-
servations have been reported by Müller et al. (2010) from
the Central Oyu Tolgoi and Zesen Uul deposits in Mongolia
and by Chang et al. (2018) from the Yulong deposit in China.
The younger quartz type at these deposits exhibits oscillatory
growth banding or wavy banding and is equivalent to QB of
this study. At Santa Rita, the rare QB crystals lining C veins can
be viewed as microscopic B veins that have been reopened
during the formation of the Cu mineralization as suggested by
Monecke et al. (2018, 2019).
Based on optical CL characteristics, fluid inclusion petrog-
raphy, and trace element abundances, two subtypes of QB
are recognized at Santa Rita. The earlier QBE hosts abundant
hypersaline liquid and vapor-rich fluid inclusions, while few
hypersaline liquid inclusions are present in the later QBL. Va-
por-rich fluid inclusions are exceedingly rare in QBL. The fluid
inclusion evidence suggests that both subtypes of QB were
precipitated within the two-phase field of the H2O-NaCl sys-
tem. However, much of QBL must have formed from hyper-
saline liquids that remained after a vapor phase had escaped
(Fig. 9b), which is indicated by the homogenization behav-
ior of many of the fluid inclusions involving homogenization
by halite disappearance. The smaller size of the salt crystals
in the hypersaline liquid inclusions hosted in QB when com-
pared to many of the hypersaline liquid inclusions present
in QA suggests that the hypersaline liquid forming QB was of
lower salinity (Klyukin et al., 2019). Inspection of the phase
relationships in the H2O-NaCl system (Monecke et al., 2018;
Klyukin et al., 2019) shows that the salinity of the hypersaline
liquid produced as a result of phase separation decreases with
temperature, confirming that the transition from QA to QB re-
cords cooling of the magmatic-hydrothermal system.
The formation of QB at Santa Rita occurred as the host
granodiorite was cooling below the transition from ductile
to brittle behavior, which occurs at ~400°C in silicic rocks
in hydrothermal systems (Fournier, 1991, 1998). Early dur-
ing this transition, and at least temporarily sealed conditions,
the hypersaline liquid and the vapor produced as a result of
phase separation were cotrapped in the QBE (Fig. 9b). The
younger QBL contains rare hypersaline liquid inclusions and
exceedingly rare vapor-rich inclusions, as the quartz presum-
ably formed under conditions where a throughgoing fracture
network was developed in such a way that the buoyant vapor
phase was physically separated from the dense, sluggish hy-
persaline liquid. The QBL precipitated during cooling of the
hypersaline liquid that was initially formed in the two-phase
 1280
field of the H2O-NaCl system (Fig. 9b). The textural evidence
suggests that gaping fractures developed during QB formation
and that these remained open long enough to allow formation
of the euhedral quartz. The transition from ductile to brittle
behavior of the wall rocks and the development of open frac-
ture networks must have been accompanied by a drop in pres-
sure from lithostatic to hydrostatic conditions (Gustafson and
Hunt, 1975; Fournier, 1991, 1998; Monecke et al., 2018; Sun
et al., 2020). The phase relationships in the H2O-NaCl system
dictate that the phase separation producing the hypersaline
liquid and coexisting vapor must have occurred at hydrostatic
pressures, as single-phase conditions extend toward lower
pressures with decreasing temperature (Fig. 9b). Formation
of QB at hydrostatic conditions is also supported by the fact
that visual evidence for postentrapment modification of most
of the fluid inclusion assemblages in QB is absent.
The nature of the hydrothermal alteration associated with
QB deposition is not well established at Santa Rita. Potassic
alteration of the host rocks occurred during QA formation.
Sulfide deposition postdating QB formation was associated
with chlorite plus K-feldspar alteration of the host rocks. The
textural evidence suggests that the magmatic-hydrothermal
fluids forming QB quartz was K-feldspar stable. This agrees
with observations at El Salvador in Chile (Gustafson and
Hunt, 1975). These authors noted that B veins at this deposit
are not associated with notable alteration halos but crosscut
host rocks that have experienced earlier pervasive potassic al-
teration.
Hypogene ore formation
The evidence presented by Nielsen (1968) indicates that Cu
mineralization at Santa Rita did not occur as early in the evo-
lution of the magmatic-hydrothermal system as A veins and
the associated potassic alteration. The relative abundance of
A veins is not correlative with high Cu grades. Ore zones at
Santa Rita are characterized by the abundance of thin C veins
that crosscut the earlier A veins and by the mineralized grano-
diorite containing disseminated sulfides. At the microscopic
scale, disseminated sulfides commonly occur along micro-
fractures cutting the host rock and the early formed A veins.
Similar observations have been made at other porphyry de-
posits where C veins account for much or all of the hypogene
ore (Dilles and Einaudi, 1992; Gustafson and Quiroga, 1995;
Manske and Paul, 2002; Xiao et al., 2011; Sapiie and Closs,
2013; Stefanova et al., 2014; Sun et al., 2020).
The narrow C veins at Santa Rita are almost entirely com-
posed of pyrite and chalcopyrite (Nielsen, 1968), although
traces of molybdenite can be present. When broken open, the
sulfide minerals coat fracture surfaces similar to the charac-
teristics of C veins described by Fournier (1967) from Liberty
in Nevada, Stefanova et al. (2014) from Elatsite in Bulgaria,
and Sun et al. (2020) from Yulong in China. In many cases,
chalcopyrite and pyrite are sprinkled along the fracture sur-
faces. At Santa Rita, the C veins are characterized by a lack
of quartz. Quartz is only present where the C veins crosscut
earlier A veins or reopen fractures that contain minor QB as
described above. In both cases, the quartz texturally predates
the sulfide minerals.
As the C veins at Santa Rita and similar sulfide veins in other
porphyry deposits (Pollard and Taylor, 2002; Sapiie and Closs,
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TSURUOKA ET AL.
2013; Stefanova et al., 2014; Braxton et al., 2018) do not con-
tain quartz that coprecipitated with the sulfide minerals, the
conditions of C vein formation cannot be directly constrained
through fluid inclusion studies. For this reason, reconstruc-
tion of the conditions of mineralization at Santa Rita had to
be based on indirect evidence. In this contribution, the fluid
inclusion inventory in quartz formed prior to the sulfides is
compared to the fluid inclusion signature of quartz precipitat-
ed after the mineralizing event. The careful paragenetic stud-
ies at Santa Rita reveal that QBL represents the last quartz type
formed prior to the deposition of the sulfide minerals. The
QBL contains hypersaline liquid inclusions and exceedingly
rare vapor-rich inclusions. The QBL is crosscut by secondary
intermediate-density fluid inclusions. Deposition of sulfides
in the C veins was postdated by the formation of the D veins
at Santa Rita. The only fluid inclusion type recognized in QD
is liquid-rich fluid inclusions, which form primary and second-
ary fluid inclusion assemblages.
The petrographic relationships suggest that sulfide forma-
tion at Santa Rita marked a significant change in the nature of
the magmatic-hydrothermal system. The QBL was deposited
from hypersaline liquids produced in the two-phase field of
the H2O-NaCl system. The lack of postentrapment modifi-
cation textures and the scarcity of vapor-rich fluid inclusions
suggest that the QBL formed at hydrostatic conditions in a
throughgoing fracture network, allowing the escape of the
vapor phase produced by phase separation. The QBL is cross-
cut by intermediate-density fluid inclusions entrapped under
single-phase conditions in the H2O-NaCl system. The lack of
postentrapment modification textures of these inclusions also
suggests entrapment at hydrostatic conditions. Inspection of
the phase relationships in the H2O-NaCl system indicates that
such a change from two-phase to single-phase conditions can
only occur as a result of a temperature decrease of the mag-
matic-hydrothermal system at hydrostatic pressure (Fig. 9c).
Deposition of sulfide minerals under brittle conditions in a
hydrostatic pressure regime is consistent with the observation
that the C veins represent hairline fractures that are coated
by sulfide minerals. Quartz precipitation after sulfide deposi-
tion took place within the single-phase field of the H2O-NaCl
system but at lower temperatures, as indicated by the higher
density of the entrapped liquid-rich fluid inclusions. Temper-
atures of homogenization measured for the liquid-rich fluid
inclusions in the D veins range up to ~360°C (Reynolds and
Beane, 1985), providing a lower temperature constraint on
the conditions of Cu mineralization.
The observation that the precipitation of QBL was postdated
by the passage of intermediate-density magmatic-hydrother-
mal fluids is of significance, as these fluids are most likely re-
sponsible for the hypogene Cu mineralization at Santa Rita.
The importance of intermediate-density fluids at this deposit
was not recognized by the previous fluid inclusion studies (Ah-
mad and Rose, 1980; Reynolds and Beane, 1985), although
the existence of these inclusions was mentioned by Ahmad
and Rose (1980). As part of this study, microthermometric
investigations were conducted on the intermediate-density
fluid inclusions, although only few assemblages with inclu-
sions large enough to perform complete microthermometric
experiments were identified (Table 1). Microthermometry
showed that the intermediate-density fluid inclusions homog-
 SANTA RITA PORPHYRY Cu DEPOSIT, NEW MEXICO
enize at ~385° to 435°C and have salinities of <10 wt % NaCl
equiv (Table 1).
Additional important constraints on the nature of the min-
eralizing fluids at Santa Rita are provided by the fact that
quartz is essentially absent in the C veins or, where pres-
ent, is paragenetically earlier than the sulfide minerals and
is corroded in contact with the sulfide phases. This implies
that sulfide precipitation occurred at conditions of retro-
grade quartz solubility (Fig. 9c). Quartz solubility modeling
by Monecke et al. (2018, 2019) showed that retrograde solu-
bility occurs in intermediate-density fluids having salinities of
<10 wt % NaCl equiv and low CO2 contents (<2 mol %) as a
result of cooling. In contrast to the intermediate-density fluid
inclusions observed to crosscut QBL, retrograde quartz solu-
bility does not occur in high-salinity fluids (Monecke et al.,
2018), ruling out that the hypersaline liquids that formed QBL
also could have formed the sulfide minerals in the C veins.
The C veins at Santa Rita are associated with alteration ha-
los containing chlorite and K-feldspar. Thermodynamic mod-
eling shows that chlorite and K-feldspar coexistence occurs at
~300°C and 1,000 bar (Seedorff et al., 2005) and transitions
toward higher temperatures at lower pressures (Beane and Ti-
tley, 1981). This is broadly consistent with the conclusion that
the Cu mineralization at Santa Rita formed at temperatures
exceeding ~360°C but below the ductile to brittle transition.
Given the range of homogenization temperatures observed
for the intermediate-density fluid inclusions and the quartz
solubility constraints, Cu mineralization appears to have oc-
curred at maximum temperatures of ~450°C.
Origin of the Whim Hill breccia
The Whim Hill breccia, located in the north-central part of
the Santa Rita stock, was a large elliptical breccia body. The
breccia contained angular blocks of the stock, some of which
hosted A veins. This provides unequivocal evidence that brec-
cia formation postdated early quartz vein formation. Breccia
formation was followed by the deposition of quartz crystals
into the open space created. Based on fluid inclusion evi-
dence, optical CL imaging, and trace element analysis, the
large euhedral quartz crystals in the Whim Hill breccia are
mostly composed of QBL.
The Whim Hill breccia presumably formed either when or
after the Santa Rita stock transitioned from ductile to brittle
behavior. In contrast to the process suggested by Norton and
Cathles (1973), formation of the Whim Hill breccia likely oc-
curred as a result of rapid decompression and escape of over-
pressured magmatic-hydrothermal fluids (cf. Sillitoe, 1985),
perhaps during a pressure blowout from the lithostatic to the
hydrostatic region (Fournier, 1991). The observation that QBL
grew into open space and the fluid inclusion inventory of the
quartz suggest that hydrostatic conditions were established
before or during the precipitation of QBL.
Following breccia formation and initial deposition of QBL,
QD was precipitated as the latest growth zones of the large
euhedral quartz crystals in the Whim Hill breccia. The outer
growth zones of QD contain chlorite aggregates and rosettes.
The K-feldspar present in potassic-altered rock fragments is
not altered, suggesting that the magmatic-hydrothermal fluid
forming the quartz was K-feldspar stable. This implies that
quartz formation in the Whim Hill breccia occurred initially
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by Raymond Rivera Cornejo
1281
under conditions of chlorite and K-feldspar stability, which
is the alteration assemblage stable during the formation of
the hypogene copper mineralization. During continued fluid
evolution, chlorite-sericite and sericite were stabilized. The D
veins at Santa Rita are associated with sericite alteration. This
difference in alteration style likely reflects a change in fluid
acidity, which is controlled by fluid/rock ratio and tempera-
ture (cf. Seedorff et al., 2005).
Late quartz vein formation
The formation of the D veins at Santa Rita postdated the
mineralizing event, as these veins are barren and crosscut all
earlier vein types. The QD in these late veins contains only liq-
uid-rich fluid inclusions, demonstrating that quartz formation
occurred in the single-phase field of the H2O-NaCl system
(Fig. 9d). Microthermometric investigations on the liquid-
rich fluid inclusions by Reynolds and Beane (1985) yielded
homogenization temperatures of 260° to 360°C and salinities
of up to 9 wt % NaCl equiv.
The host rocks of the D veins were brittle during QD pre-
cipitation, resulting in the formation of planar veins. Hydro-
static conditions prevailed within the interconnected fracture
network, now occupied by the D veins. At the temperatures
of QD formation, quartz precipitation occurred as a result of
cooling of the magmatic-hydrothermal fluids (Fig. 9d). The
liquid could have undergone intermittent dilution by ambient
meteoric water, possibly explaining the observed variations in
the salinity and homogenization temperatures of the liquid-
rich fluid inclusions (cf. Reynolds and Beane, 1985). However,
isotopic studies performed on the sericite alteration halos of
other porphyry deposits suggest that influx of meteoric water
is probably minimal and that fluid mixing may be restricted to
the marginal sericite alteration (Hedenquist et al., 1998; Har-
ris and Golding, 2002).
Implications
The hypogene Cu sulfide mineralization at Santa Rita oc-
curred after the host intrusion underwent potassic alteration
during the early formation of A veins. At the deposit scale,
Nielsen (1968) showed that ore grade does not directly cor-
relate with the occurrence of A veins and the distribution of
potassic alteration. Establishment of crosscutting relation-
ships at the hand specimen scale illustrated that the C veins
consistently crosscut the earlier A veins (Nielsen, 1968). Tex-
tural relationships suggest that Cu sulfides, where present
within earlier A veins, postdate the high-temperature quartz
and were introduced after the A vein formation, presumably
because of reopening of the existing veins at the same time
as the C veins were formed. At a microscopic scale of obser-
vation, critical textural relationships proving coprecipitation
of quartz and Cu sulfides, such as the occurrence of sulfide
inclusions encapsulated along growth bands in quartz, have
never been encountered at Santa Rita. Quartz in contact
with the Cu sulfide minerals commonly shows irregular grain
boundaries, suggesting that sulfide deposition was accompa-
nied by quartz dissolution.
Although sulfide veins resembling the C veins at Santa
Rita have been previously reported to occur at other depos-
its (Fournier, 1967; Pollard and Taylor, 2002; Arif and Baker,
2004; Sapiie and Closs, 2013; Stefanova et al., 2014; Braxton
 1282
et al., 2018; Rinne et al., 2018; Sun et al., 2020), there is cur-
rently no consensus as to the general importance of this vein
type. The observations at Santa Rita suggest that the relative
importance of these veins in porphyry deposits is probably
underappreciated. The C veins are unassuming in nature,
as most are hairline fractures coated by Cu sulfide minerals
forming paint on the fracture surfaces (cf. Fournier, 1967), as
opposed to classic stockwork veins that formed through infill
of gaping fractures.
At Santa Rita, the C veins are associated with chlorite plus
K-feldspar alteration. This alteration style overprints the ear-
lier potassic alteration (Reynolds and Beane, 1985). In hand
specimen, the chlorite and K-feldspar alteration associated
with these veins could be easily mistaken for potassic altera-
tion if the fine-grained, dark chlorite is misidentified as bio-
tite or, alternatively, the chlorite could be misinterpreted as
part of a late intermediate argillic overprint. It is important
to note that despite careful study, Nielsen (1968) misidenti-
fied the fine-grained chlorite as green biotite in the field. Cor-
rect identification of the alteration style associated with the
C veins at Santa Rita required thin section petrography and
electron microprobe analysis (Reynolds and Beane, 1985).
Staining with sodium cobaltinitrite commonly applied to sup-
port field investigations (Duuring et al., 2009; Byrne et al.,
2020; Cooke et al., 2020) may not provide conclusive insights
into the nature of alteration associated with the C veins, as
K-feldspar occurs in the potassic-altered rock as well as in the
chlorite plus K-feldspar alteration.
The current study suggests that single-phase, magmatic-
hydrothermal fluids having a critical or near-critical density
(critical density of a 5 wt % NaCl fluid is 0.48 g/cm3; Monecke
et al., 2018) caused the Cu mineralization at Santa Rita as they
escaped from lithostatic to hydrostatic conditions and cooled.
Secondary fluid inclusions of this fluid type crosscut the last
quartz formed prior to the precipitation of the Cu sulfide
minerals. The careful petrographic investigations show that
intermediate-density fluid inclusions do not occur in quartz
formed after the Cu sulfides. This observation provides evi-
dence for the relative timing of passage of these fluids through
the Santa Rita deposit. Quartz solubility modeling shows that
the lack of quartz as a gangue mineral in the C veins and the
occurrence of dissolution textures of quartz in contact with
Cu sulfides can be explained by the retrograde solubility of
quartz in intermediate-density fluids. This provides strong ev-
idence for the nature of the mineralizing fluids, as other fluid
types, in particular high-salinity liquids commonly invoked
to be responsible for mineralization in porphyry deposits, do
not cause retrograde quartz solubility (Monecke et al., 2018).
Thermodynamic modeling also shows that intermediate-den-
sity fluids with near-critical densities are particularly suited as
ore-forming fluids, as they have distinctively high mass and
energy transport capacities (Norton and Knight, 1977; John-
son and Norton, 1991; Norton and Dutrow, 2001; Klyukin et
al., 2016). The findings at Santa Rita support previous studies
hypothesizing that Cu sulfide formation in porphyry deposits
occurs primarily as a result of fluid cooling over a narrow tem-
perature range that broadly overlaps with the ductile-brittle
transition of the host rocks (Redmond et al., 2004; Klemm et
al., 2007; Landtwing et al., 2010; Kouzmanov and Pokrovski,
2012; Stefanova et al., 2014; Monecke et al., 2018; Sun et al.,
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by Raymond Rivera Cornejo
TSURUOKA ET AL.
2020). At Santa Rita, there is no evidence for remobilization
of Cu from A veins into the ore shell from what would now
be a barren or subeconomic part of the deposit (cf. Brimhall,
1979). There are no supporting observations that Cu sulfides
had ever precipitated at high temperatures or textural rela-
tionships that might indicate dissolution of previously existing
Cu sulfides.
Conclusions
This study reexamined the paragenetic relationships of stock-
work veins at the Santa Rita porphyry copper deposit, New
Mexico, to determine the evolution of the magmatic-hydro-
thermal system that formed this deposit and to determine the
conditions at which hypogene ore formation took place. A
range of analytical techniques was employed, including fluid
inclusion petrography, optical CL microscopy, and trace ele-
ment analysis by electron microprobe, to distinguish the dif-
ferent quartz types formed before and after the mineralizing
event. The careful petrographic investigations indicate that
Cu mineralization at Santa Rita postdated the early high-tem-
perature vein formation and the associated potassic alteration.
At Santa Rita, the Cu mineralization occurs in sulfide veins
that lack quartz as a gangue mineral. The paucity of quartz as
a coprecipitate with the Cu sulfide minerals hampers direct
identification of the conditions of sulfide formation through
fluid inclusion studies. This study demonstrates that important
constraints on the nature of the mineralizing fluids can still be
derived based on the comparison of the fluid inclusion inven-
tory in quartz formed prior to and after the Cu mineralization.
Based on this comparison, the Cu mineralization at Santa Rita
is interpreted to have occurred from a single-phase, low-sa-
linity (<10 wt % NaCl equiv), magmatic-hydrothermal fluid
of critical or near-critical density at temperatures exceeding
~360°C but below ~450°C.
Acknowledgments
We are indebted to H. Lowers, D. Adams, and M. Bennett
for help provided during the electron microprobe investiga-
tions at the U.S. Geological Survey in Denver, Colorado. L.
Fisher and T.O. Wyatt are thanked for assistance provided
during the FE-SEM investigations. This study benefited from
discussions with A. Gysi, E. Holley, and K. Pfaff on the geo-
chemistry of magmatic-hydrothermal systems. The research
formed part of a Ph.D. study by ST that was financially sup-
ported by Japan Oil, Gas and Metals National Corporation.
We thank an anonymous reviewer and D. Cooke for insightful
reviews that helped us to improve an earlier version of this
manuscript. D. Cooke is also thanked for editorial handling of
the manuscript.
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Subaru Tsuruoka is an economic geologist
with experience working on multiple ore deposit
types including porphyry copper, epithermal
gold, and sediment-hosted copper deposits. He
completed his B.Sc. and M.Sc. degrees at Tokyo
Institute of Technology and subsequently worked
as a project geologist based in Tokyo. In 2017,
Subaru obtained his Ph.D. degree from Colorado School of Mines. He is
currently a postdoctoral research fellow based at iCRAG, the Irish Centre
for Research in Applied Geosciences at University College Dublin, Ireland.
His postdoctoral research focuses on the stratigraphic and structural architec-
ture of sedimentary basins and their endowment of sediment-hosted copper
deposits.