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Fluid Inclusion Chemistry of Adularia-Sericite

Epithermal Au-Ag Deposits of the Southern
Hauraki Goldfield, New Zealand

Article in Economic Geology · May 2015

DOI: 10.2113/econgeo.110.3.763

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Economic Geology, v. 110, pp. 763–786

Fluid Inclusion Chemistry of Adularia-Sericite Epithermal Au-Ag Deposits of

the Southern Hauraki Goldfield, New Zealand*
Mark P. Simpson,1,** Sabina Strmic Palinkas,1,† Jeffrey L. Mauk,2 and Robert J. Bodnar3
1 School of Environment, University of Auckland, Private Bag 92019, Auckland, New Zealand
2 U.S. Geological Survey, P.O. Box 25046, MS-973, Denver, Colorado 80225-0046
3 Department of Geosciences, 4044 Derring Hall, Virginia Tech, Blacksburg, Virginia 24061

Abstract
Microthermometry, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), and Raman
spectroscopy have been used to determine the temperature, apparent salinity, and composition of individ-
ual fluid inclusions in adularia-sericite Au-Ag epithermal veins from the Karangahake, Martha, Favona, and
­Waitekauri deposits, southern Hauraki goldfield, New Zealand. Quartz veins contain colloform to crustiform
bands that alternate with coarse-grained quartz and amethyst. The ore mineralization occurs only in colloform
to crustiform bands.
Analyses of individual fluid inclusions by LA-ICP-MS identify Na as the most abundant cation, together
with variable concentrations of K, Ca, Rb, Sr, Sb, and As. Rare inclusions have detectable Li, Al, and Ba con-
centrations, although recorded Al concentrations with values up to 231 ppm in Al-free quartz may reflect an
accidentally captured mineral phase rather than fluid itself. The Na content ranges from ~260 to 10,200 ppm
for inclusions in quartz and ~9,700 to 13,700 ppm for inclusions in amethyst. Antimony is the second most com-
monly detected element in both quartz- and amethyst-hosted inclusions; this element is also detected in the
host mineral. Concentrations of Sb and As range from 0.3 to 988 ppm and from 3.33 to 418 ppm, respectively,
and are most commonly detected in inclusions from the Karangahake and Martha deposits. The poor correla-
tion between the Na content with either Sb or As suggests that Sb and As were transported as neutral hydroxyl
complexes of Sb(OH)3 and As(OH)3. Both Au and Ag occur at concentrations that are less than their respective
detection limits (ppm).
Geochemical modeling of the microthermometric and LA-ICP-MS data obtained from individual fluid inclu-
sions suggests that fluids responsible for the quartz deposition were neutral to alkaline and that adiabatic boiling
is the most effective mechanism for both gold and silica precipitation. The presence of single-phase vapor-only
fluid inclusions in some mineralized samples indicates that local flashing may have contributed to deposition
of Au and Ag.
Assuming adiabatic boiling under hydrostatic pressure, samples from the Karangahake deposit (Maria vein)
were deposited from low-salinity fluids (<3.9 wt % NaCl equiv) at temperatures between 225° and 262°C and at
depths of 270 to 575 m below the former water table. The average deep reservoir fluid temperature estimated
from the Na/K geothermometer is 287°C, and the steam loss during boiling ranges between 8 and 17%.
Fluid inclusions in quartz from the Martha deposit trapped dilute fluids with salinity less than 1.7 wt % NaCl
equiv. The coexisting liquid-rich (homogenization temperature, Th = 189°−225°C) and vapor-rich inclusions (Th
= 205°−243°C) suggest formation at depths of 200 to 400 m below the water table. According to the Na/K geo-
thermometer, the deep reservoir fluid temperature was near 295°C, and the steam loss during boiling ranged
between 15 and 23%. Pseudosecondary inclusions in amethyst display salinity around 4.0 wt % NaCl equiv
and homogenization temperatures between 218° and 241°C. Secondary inclusions are slightly more dilute
(3.2−4.2 wt % NaCl equiv), with homogenization temperatures between 213° and 242°C.
Fluid inclusions in quartz from the Waitekauri deposit homogenize from 210° to 265°C and contain less than
1.2 wt % NaCl equiv. A thin quartz vein that occurs between the Jubilee and Scotia deposits contains coexist-
ing liquid- and vapor-rich inclusions; their homogenization temperatures indicate a formation depth of 300 m
below the former water table. The calculated deep reservoir fluid temperature is around 283°C and the steam
loss is estimated to be between 13 and 18%.
LA-ICP-MS analyses show that in some cases different fluid inclusion assemblages (FIAs) within a single
sample trapped fluids with variable chemistries. These differences likely reflect modification of a single parent
fluid through mineral dissolution and precipitation, water/rock interactions, boiling and vapor loss, conductive
cooling, and mixing.

Introduction approximately 50 adularia-sericite epithermal Au-Ag depos-

The Hauraki goldfield is located in the Coromandel Penin-
sula of the North Island of New Zealand (Fig. 1). It contains
*A digital supplement to this paper is available at http://economicgeology.
org/ and at http://econgeol.geoscienceworld.org/.
**Current address: GNS Science, Wairakei Research Centre, 114 Kare-
toto Road-RD4, Taupo 3377, New Zealand.
† Corresponding author, e-mail: s.strmic-palinkas@auckland.ac.nz
0361-0128/15/4305/763-24 763
its with the total past production exceeding 335,000  kg
(11 Moz) Au and 1.6 million kg (51 Moz) Ag (Christie et al.,
2007; Mauk et al., 2011). Mineralization is predominantly
hosted by hydrothermally altered andesite and dacite of the
Coromandel volcanic zone and is related to early Miocene
to late Pliocene subaerial hydrothermal systems (Skinner,
1986).
Submitted: February 25, 2014
Accepted: August 13, 2014
764 SIMPSON ET AL.

176°E
Hauraki
Goldfield
Auckland
38°S
0 200 km
0 20 km
Alluvial sediments
(Quaternary)
Whitianga Group
(Pliocene - Pleistocene)
rhyolites and ignimbrites
Coromandel Group
(L. Miocene - Pliocene)
andesites and dacites
Coromandel Group
(L. Miocene)
diorite intrusives
Manaia Hill Group
(Jurassic)
metagreywacke
Major fault
al., 1998; Klemm et al., 2007; Kouzmanov et al., 2010; Appold
175°5´E
N and Wenz, 2011). In contrast, studies dealing with the compo-
sition of low-salinity fluids are not common (e.g., Rusk et al.,
Great Barrier 2004; Wallier et al., 2006), owing to the poor analytical preci-
Island sion obtained during analysis of low-salinity fluids.
This study documents the composition of individual low-
salinity fluid inclusions (<5 wt % NaCl equiv) in quartz veins
from the Karangahake, Waitekauri, Favona, and the world-
class Martha adularia-sericite epithermal Au-Ag deposits in
Coromandel the Hauraki goldfield, New Zealand (Fig. 1), as determined
Peninsula
by a combination of microthermometry, LA-ICP-MS, and
Raman spectroscopic analyses. The aim of the paper is to
constrain the composition of the inclusion fluids, estimate the
principal differences in the composition of primary, pseudo-
secondary, and secondary fluid inclusions, and compare the
composition of inclusion fluids with the reservoir fluids in
geothermal fields from around the world. Furthermore, the
37°0´S estimation of the formation conditions and chemistry of the
mineralizing fluids should provide better insight into the gen-
esis of adularia-sericite epithermal Au-Ag veins.
Regional and Local Geology
Epithermal Au-Ag deposits of the Hauraki goldfield occur
Waitekauri
Martha &
in the Coromandel volcanic zone (Fig. 1), a subaerial Miocene
Karangahake Favona to Pliocene (~18−1.95 Ma) volcanic arc formed due to con-
vergence along the Pacific-Australian plate boundary (Skin-
ner, 1986; Nicholson et al., 2004; Mortimer et al., 2007). The
Ha

Epithermal Au-Ag deposit Coromandel volcanic zone consists of andesite, dacite, rhyo-
ura

lite, and minor basalt that unconformably overlie Mesozoic

ki

Porphyry Cu+Au±Mo occurrence

Rift

metasediments of the Manaia Hill Group. Andesite and dacite

Fig. 1. Geologic map of the Hauraki goldfield, showing the locations of
the Karangahake, Martha-Favona, and Waitekauri deposits (after Skinner,
1986; Christie et al., 2007). The symbols used to represent the epithermal
deposits are oriented to the main vein strike direction. Inset shows the loca-
tion of the Hauraki goldfield within the North Island of New Zealand.
Previously published fluid inclusion data from the Hauraki
goldfield epithermal Au-Ag deposits suggest that hydrother-
mal fluids responsible for mineralization were dilute (up to
2.4 wt % NaCl equiv, minor CO2), near-neutral pH, reduced,
and locally boiling (Simpson et al., 2001; Brathwaite and
Faure, 2002; Christie et al., 2007; Simpson and Mauk, 2007,
2011). The depositional temperatures are estimated to range
between 190° and 295°C (Christie et al., 2007). Fluid inclu-
sion studies from many adularia-sericite epithermal Au-Ag
deposits worldwide have shown similar characteristics (e.g.,
epithermal Au-Ag deposits in West Java, Indonesia: Marcoux
and Milési, 1994; McLaughlin, California: Sherlock et al.,
1995; Hishikari, Japan: Etoh et al., 2002; Guanajuato, Mexico:
Moncada et al., 2012; Bodnar et al., 3014; Mango et al., 2014).
Despite numerous and detailed studies of fluid inclusions in
epithermal deposits that represent preserved remains of the
ore-forming fluids, the chemical composition of these fluids
is poorly known. Although laser ablation-inductively coupled
plasma-mass spectrometry (LA-ICP-MS) is an efficient multi-
element microanalytical technique for determining the in-situ
elemental concentrations of individual fluid inclusions (Gün-
ther et al., 1998; Heinrich et al., 2003; Pettke et al., 2012;
Sirbescu et al., 2013), it has so far been mostly applied to ore
deposits characterized by high-salinity fluids (e.g., Audétat et
of the Coromandel Group (18−3.8 Ma) occur as massive
flows, autoclastic breccias, lahars, and tuffs forming a series of
stratovolcanoes in which volcanism was separated by periods
of quiescence and erosion (Skinner, 1986; Adams et al., 1994;
Booden et al., 2012). Younger rhyolitic volcanic rocks of the
Whitianga Group (11−1.5 Ma) overlie and interfinger with
andesite and dacite of the Coromandel Group and occur as
ignimbrite and lava flows related to several caldera complexes
in the central and southern parts of the Coromandel Penin-
sula (Skinner, 1986; Adams et al., 1994; Briggs et al., 2005).
The Hauraki goldfield is cut by NNW- and NNE- to ENE-
striking faults with steep to moderate dips (Spörli et al., 2006).
NNW-striking faults equally displace rocks downward to the
east and west. In contrast, most NNE-striking faults displace
rocks downward to the south, and this exposes older volca-
nic rocks and the basement metasediments in the northern
Coromandel Peninsula (Fig. 1). The Hauraki goldfield is
bounded on the west by the active NNW-trending Hauraki
rift (Hochstein and Ballance, 1993). The epithermal Au-Ag
deposits mostly occur as quartz veins that fill high-angle frac-
tures. Available kinematic data indicate that the veins formed
in extensional environments predominantly by normal dip-
slip movement (Nortje et al., 2006; Begbie et al., 2007; Spörli
and Cargill, 2011).
Karangahake deposit
The Karangahake deposit is the third largest Au producer in
the Hauraki goldfield, with historical production from 1882 to
1944 of 29,425 kg (0.95 Moz) Au and 97,290 kg (3.13 Moz) Ag
(Christie et al., 2007). More recent exploration has identified a
 ADULARIA-SERICITE EPITHERMAL Au-Ag DEPOSITS, S. HAURAKI GOLDFIELD 765

resource of 5,670 kg (0.2 Moz) Au and 22,680 kg (0.7 Moz) Ag the area of strong hydrothermal alteration where magnetite
(Stevens and Boswell, 2006). Quartz veins are hosted mainly has been destroyed (Harris et al., 2005).
by andesite that is locally capped by rhyolite. The veins are The main veins of the Karangahake deposit are the N- to
surrounded by a 4.2- × 2.7-km (~6 km2) demagnetized zone NE-striking Maria and Welcome/Crown veins (Fig. 2A). The
delineated by the aeromagnetic anomaly and corresponds to Maria vein has a known strike length of 1,300 m, a vertical

A Karangahake C Martha-Favona N

N
Open pit
outline
a
rth e
Ma pir
Em

ona
l

Fav
ya
Ro

ome

Sil
ion

ver
Welc Un

ton
io
Tr
th
an

t
nligh
r
Ama

Moo
0 1 km
Maria

1090
D Martha - Favona section
NW SE
Crown

Martha
(open pit)
Welcome

0 m RSL

Union

nth
re
pi

Trio
gh

ara
Em

Fa
ou

Am

vo
dn

Reptile
yal

na
ea
Mar

Ro
Dr
tha

Mt Karangahake -500 m RSL

(544 m) Ignimbrite
Dacite
0 500 m 0 500 m
Andesite

B Karangahake longitudinal section along Maria vein E Waitekauri N

N S
Jubilee
Jasper Creek
400 m RSL
Dubbo
Shoot

Scotia
oot

Leached oxidized ore

ot
n Sho

Sovereign
h
nza S

200 m RSL
a Fault
a

ult
Talism

Bona
Woodstock

Partially oxidized and

i Fa

secondary enriched ore

Owharo
shoot

0 m RSL
aur

Scimitar
itek

Primary sulfide ore

Teutonic
Wa

Level 16
-200 m RSL

0 200 m 0 1 km
slope Drill hole

F
6420800 m N
Jubilee

250mRL
Scotia

Andesite
0mRL
Rhyolite
Dacite
0 250 m

Fig. 2. A. Vein maps of the Karangahake deposit surface (Stevens and Boswell, 2006). B. The longitudinal section of the
Maria vein (modified Henderson and Bartrum, 1913; Brathwaite, 1989). C. and D. Martha and Favona deposits surface and
cross section (Torckler et al., 2006). E. Waitakauri deposits and prospects surface. F. The longitudinal section of the Jubilee
deposit (Simpson and Mauk, 2011).
766 SIMPSON ET AL.

extent that exceeds 700 m, and an average width of 2 to 3 m.
The Welcome vein and its footwall branch, the Crown vein,
have a strike length of 1,100 m, an average thickness of 0.2
to 0.6 m, and they were mined over a 300-m vertical inter-
val. Veins mostly consist of crustiform-banded quartz together
with lesser vein breccias and local quartz after platy calcite;
the veins have rare cavities lined by comb quartz (Fig. 3A-C).
Gold and silver mineralization in the quartz veins is typically
disseminated, microscopic, and associated with specific bands
of massive to very fine grained quartz (Fig. 3D). In the upper
levels the veins are strongly oxidized and contain quartz, limo-
nite, Mn oxides, and electrum. Below this, partly oxidized sec-
ondarily enriched ore extends over a 150-m vertical interval.
This is characterized by quartz veins with primary sphalerite,
galena, pyrite, chalcopyrite, electrum, and acanthite over-
printed by minor to moderate amounts of secondary goethite,
Mn oxides, covellite, bornite, and chalcocite; patches of very
rich secondary ore have acanthite, gold, and wire silver. At
depth, unoxidized quartz veins contain greater amounts of
sphalerite and galena, as well as pyrite, chalcopyrite, elec-
trum, and rhodochrosite (Brathwaite, 1989). A quartz vein
stockwork (Fig. 2B) occurs in the 200-m-thick silicified rhyo-
lite cap that forms Mount Karangahake.
Previous studies of fluid inclusions hosted in quartz deter-
mined a homogenization temperature (Th) range of 168° to
310°C and apparent salinities of less than 2.7 wt % NaCl equiv
(Christie, 1982; Apthorpe et al., 1986; Brathwaite, 1989).
Martha and Favona deposits (Waihi vein system)
The Martha and Favona deposits are part of a series of veins
that are collectively known as the Waihi vein system (Fig.
2C-D). The Martha deposit was worked as an underground
mine from 1883 through 1952, and it has been mined as an
open pit since 1988. This world-class epithermal deposit has
produced more than 210,944 kg (6.8 Moz) Au and 1.30 mil-
lion kg (42 Moz) Ag (Mauk et al., 2011). The nearby con-
cealed Favona deposit, located less than 2 km to the east, has
produced a further 11,300 kg (0.4 Moz) of Au and 317,500 kg
(10 Moz) of Ag (Richards, 2011). Both deposits are hosted by
andesite and are enclosed in a single 10-km2 zone of hydro-
thermal alteration (Morrell et al., 2011). The 40Ar/39Ar dates
for vein adularia from Martha (6.12 ± 0.03 Ma) and Favona
(6.05 ± 0.04 Ma) overlap within error (Mauk et al., 2011).
Host rocks at Martha and Favona are altered to quartz, adu-
laria, illite, interstratified illite-smectite, and pyrite with minor
chlorite, albite, and calcite (Brathwaite and Faure, 2002; Cas-
tendyk et al., 2005, Simpson and Mauk, 2007). Quartz veins
at Martha form a complex braided pattern in plan and cross
section and extend 1.6 km along strike in a zone up to 500 m
wide and mined to a depth of 575 m below surface (Morgan,
1924; Brathwaite and Faure, 2002; Spörli and Cargill, 2011).
There are four main subparallel NE-striking quartz veins
(Martha, Welcome, Empire, and Royal); the Martha vein is
up to 25 m wide and dips southeast, whereas most other veins
dip northward, converging with the Martha vein at depth.
The concealed Favona vein occurs near the historically mined
Union, Amaranth, Silverton, and Old Favona veins (Torckler
et al., 2006). The Favona vein has a strike length of 1 km, a
vertical extent exceeding 400 m, and is on average 1 to 3 m
wide. Quartz veins at Martha are predominantly crustiform
banded but massive and brecciated veins occur as well (Fig.
3E). Cavities are commonly lined by drusy, comb, and locally
elongated quartz crystals that range up to several centime-
ters in length. The principal vein mineral is quartz with local
adularia, calcite, kaolinite, chlorite, corrensite [(Ca,Na,K)
(Mg,Fe,Al)9(Si,Al)8O20(OH)10⋅n(H2O)], plus late amethyst
and innesite [Ca2Mn7Si10O28(OH)2⋅5(H2O)] (Brathwaite and
Faure, 2002). Most veins contain pyrite, sphalerite, galena,
chalcopyrite, and electrum (Fig. 3F). Base metal sulfide min-
erals tend to increase with depth. Other ore minerals include
tetrahedrite, acanthite, aguilarite [Ag4SeS], stromeyerite
[CuAgS], naumannite [Ag2Se], and mckinstryite [(Ag,Cu)2S],
but these have more localized distributions (Mauk et al.,
2011). Amethyst is a minor but distinctive phase and marks
a late event in the vein deposition sequence. Veins at Favona
are predominantly colloform banded. Similar to Martha, cavi-
ties are usually filled with elongated quartz crystals (Fig. 3G).
Previous studies of fluid inclusions hosted by quartz and cal-
cite from the Martha and Favona deposits yielded Th values
from 141° to 306°C; the inclusions trapped dilute fluids with
less than 2 wt % NaCl equiv (Brathwaite and Faure, 2002;
Simpson and Mauk, 2007). Fluid inclusions in late amethyst
from Martha have a similar Th range of 170° to 253°C, but
trapped more saline fluids with up to 4.5 wt % NaCl equiv
(Brathwaite and Faure, 2002).
Waitekauri deposits and prospects
The Waitekauri area (Fig. 2E), which includes the Sover-
eign, Jubilee, and Scotia deposits and the Scimitar, Teutonic,
and Jasper Creek prospects, produced only 392 kg (12,603 oz)
Au-Ag bullion from 1875 to 1929 (Downey, 1935). The min-
eralization is hosted by andesitic and dacitic flows, breccias,
and local pyroclastic and air fall deposits of the Coromandel
Group. The veins occur in an irregular hydrothermal altera-
tion zone whose aeromagnetic signature covers 22 km2 and
also encloses the Maratoto, Golden Cross (23,504 kg Au,

Fig. 3. Images of quartz veins. A. Colloform-crustiform banded quartz vein with breccia containing mineralized sulfide
clots and overgrown by comb quartz, Maria vein level 8, Karangahake (AU 62198). B. Colloform-crustiform banded quartz
vein with concordant comb quartz layer, Maria vein level 6, Karangahake (AU 62191). C. Colloform-crustiform banded and
locally brecciated quartz vein with enclosed spray of elongated quartz crystals and stained by iron oxyhydroxides; cavities
are lined by small sprays of quartz, Welcome vein, level 8, Karangahake (AU 62232). D. Bonanza-grade quartz vein with
thin, millimeters wide, bands of electrum and chalcopyrite overgrown by cryptocrystalline quartz; cavities are lined by comb
quartz, BM37 ore shoot, Maria vein, level 8, Karangahake (sample Heritage gold). E. Several large prismatic quartz crys-
tals cemented in cryptocrystalline quartz containing disseminated pyrite, Martha deposit (AU 58166). F. Breccia rock clasts
cemented by banded cryptocrystalline quartz and dentritic sphalerite plus lesser galena overgrown by comb quartz, Martha
deposit, level 14 (AU 62242). G. Cavity with elongated quartz crystals, Favona deposit (sample AU 59032). H. Thin quartz
vein with comb crystals enveloped by fine-grained quartz, Sovereign, Waitekauri deposit (AU 59733).
 ADULARIA-SERICITE EPITHERMAL Au-Ag DEPOSITS, S. HAURAKI GOLDFIELD 767

A B

6 cm 3 cm

C D

3 cm 1 cm

E F

3 cm 3 cm

G H

2 cm 1 cm
768 SIMPSON ET AL.
73,134 kg Ag), Komata, and Grace Darling deposits (Mor-
rell et al., 2011). Even though all these deposits occur within
the same alteration envelope, different 40Ar/39Ar ages for the
Maratoto (6.41 ± 0.04 Ma), Golden Cross (6.98 ± 0.11 Ma),
Komata (6.06 ± 0.06 Ma), and Sovereign (6.70 ± 0.16 Ma)
deposits, combined with differences in alteration and vein
mineralogy (Simpson and Mauk, 2011), suggest that these
deposits formed at different times, most likely from spatially
overlapping but temporally distinct hydrothermal systems
(Mauk et al., 2011).
The main Au-Ag mineralized quartz vein is the NNE-trend-
ing Jubilee vein (Fig. 2F) that has a strike length of 990 m, a
vertical extent exceeding 215 m, and averages 2.4 m in width,
but it is strongly lenticular and commonly narrows to several
centimeters (Downey, 1935). Much of the vein contains only
minor Au and Ag associated with volumetrically minor crusti-
form-banded quartz (Hartley and McConnochie, 1991). Base
metal sulfide minerals including sphalerite, galena, and chal-
copyrite occur at depth. The quartz veins at Sovereign and
Scotia are typically narrow and rarely exceed 1 m in width
(Fig. 3H). Calcite veins are most abundant at Scotia, Scimi-
tar, and Jasper Creek and occur together with various zeolites
including laumontite, clinoptilolite, mordenite, and stilbite
(Simpson and Mauk, 2011).
Fluid inclusions in quartz and calcite homogenize between
132° and 310°C and trapped a dilute solution with an appar-
ent salinity of less than 2.6 wt % NaCl equiv. Homogenization
temperatures are highest at Sovereign (avg 241°C), Jubilee
(avg 239°C), and Scimitar (avg 236°C), lower at Scotia (avg
204°C) and lowest at Teutonic (avg 168°C), and Jasper Creek
(avg 162°C; Simpson and Mauk, 2011).
Samples and Analytical Techniques
The LA-ICP-MS analyses of individual inclusions that we
report in this study represent analyses of large fluid inclu-
sions. Inclusions less than about 10 μm across do not yield a
sufficient degree of precision. Because large fluid inclusions
are rare in epithermal deposits, we examined a large suite of
hand samples and fluid inclusion plates to select samples with
a higher proportion of large inclusions; we report results from
16 samples from the Karangahake, Martha, Favona, and Wait-
ekauri deposits (App. 1). Epithermal veins were sampled from
current and historic underground workings, drill core expo-
sures, and an open pit. Sample selection was biased toward
coarsely crystalline quartz, or euhedral quartz crystals in order
to increase the likelihood of finding suitably large fluid inclu-
sions. Measurable fluid inclusions have been found in quartz
that occurs in concordant comb bands, euhedral quartz crystals
within main-stage crustiform banded veins, and in later stage
prismatic to elongated quartz crystals that fill vugs. Some of
studied quartz crystals occur in close proximity to ore minerals
(several millimeters), and some predate ore mineral deposi-
tion. However, the quartz that is intergrown with ore minerals
is cryptocrystalline to very fine grained and lacks large fluid
inclusions. As noted by Bodnar et al. (1985) and by Moncada et
al. (2012), the silica phase that is deposited with Au and/or Ag
in epithermal deposits is rarely appropriate for trapping and
preserving fluid inclusions, requiring study of either second-
ary inclusions that can be related to mineralization or primary
inclusions in minerals that bracket precious metal deposition.
For the Karangahake deposit, we examined a suite of
56 vein samples and prepared 33 fluid inclusion plates from
27 samples. We collected Th measurements for 861 inclusions
from 24 samples, and from these, we acquired LA-ICP-MS
data for seven samples.
For the Martha deposit, we examined a suite of 230 vein
samples, and from this we selected 12 samples and pre-
pared 20 fluid inclusion plates. Most of these fluid inclusion
plates did not contain sufficiently large fluid inclusions, so we
acquired LA-ICP-MS data from only three samples.
For the Waitekauri deposits and prospects, 20 quartz vein
samples were selected for fluid inclusion measurements.
These were selected from a larger suite of 276 samples (Simp-
son and Mauk, 2011). Only five of the 20 quartz veins had
fluid inclusions that were suitable for LA-ICP-MS analyses.
Microthermometry
Fluid inclusion homogenization (Th) and final ice melting
temperatures (Tm) were obtained on fluid inclusions in 100-
to 250-μm thick doubly polished sections using a Fluid Inc.-
adapted USGS heating and freezing stage. The thermocouple
was calibrated using SYN FLINC synthetic fluid inclusion
standards (Sterner and Bodnar, 1984) at 0.0°, −56.6°, and
374.1°C, with the data reproducible to ±0.2°C for final ice
melting temperatures and ±2.0°C for homogenization temper-
atures. Apparent salinity was calculated from final ice melting
temperatures using the equation of Bodnar (1993). Heating-
freezing measurements were made on carefully defined fluid
inclusion assemblages (FIAs), representing groups of inclu-
sions that were trapped simultaneously; for example, inclu-
sions contained within an individual growth zone or a healed
fracture (Goldstein and Reynolds, 1994; Goldstein, 2001; Bod-
nar 2003). All FIAs were identified based on petrography prior
to heating and freezing. If all of the fluid inclusions within the
FIAs showed similar Th values, the inclusions were assumed
to have trapped the same fluid and to have not been modi-
fied by leakage or necking; these fluid inclusions thus record
the original trapping conditions. Although the LA-ICP-MS
measurements were conducted only on fluid inclusions larger
than 10 μm across, it should be stressed that all analyzed FIAs
contain both large and small fluid inclusions. Consequently, no
bias was introduced by choosing only large inclusions, because
they were members of FIAs that also contain small inclusions.
Multiple FIAs were measured for many of the samples: how-
ever, the relative timing of different FIAs often could not be
established because the FIAs commonly occur in spatially
separated groups in different parts of a crystal with no obvious
connection, or in different crystals of the same vein.
LA-ICP-MS
The elemental concentrations of individual fluid inclusions
were measured using the LA-ICP-MS at the Department of
Geosciences Fluids Research Laboratory at Virginia Tech.
The system features a GeolasPro Excimer 193-nm ArF laser
ablation system coupled with an Agilent 7500ce quadrupole
mass spectrometer. Samples were ablated in a 1.5-cm3 abla-
tion cell, using a laser output energy of 150 mJ and adjusting
beam diameter to ensure ablation of the entire fluid inclu-
sion. The energy density (fluence) was between 7 and 10 J/
cm2. For all inclusions, we analyzed for Na, Mg, Al, K, Ca,
 ADULARIA-SERICITE EPITHERMAL Au-Ag DEPOSITS, S. HAURAKI GOLDFIELD 769
Mn, Fe, Cu, Zn, As, Se, Rb, Sr, Ag, Sb, Te, Ba, Au, Tl, and
Pb. Data were collected in two analytical sessions, and in the
first, Ti and S were also measured for inclusions from Karan-
gahake, Martha, and Favona. In the second analytical session
for the Waitekauri deposit, Li was measured as well, and Ti
and S were excluded because in the first session the concen-
trations of these elements were below their detection limits
(average detection limits at 6.1 and 56 ppm, respectively). A
dwell time of 10 milliseconds (ms) was used for all elements,
except for S and Au, where a dwell time of 40 ms was used to
improve detection limits. Element concentrations from tran-
sient signal profiles were determined by integration of signal
intensities for all elements, correction for machine drift, com-
parison of intensity ratios with NIST glass standard SRM-610,
and referencing the ratios to the concentration of Na that was
used as an internal standard (Audétat et al., 1998; Günther
et al., 1998; Heinrich et al., 2003). Reduction of LA-ICP-MS
fluid inclusion data was carried out using the AMS software
(Mutchler et al., 2008). An independent determination of Na
concentration in the fluid inclusions was obtained from Tm
values, which were converted to wt % NaCl equiv, using the
equation of Bodnar (1993). Wt % NaCl equiv was then con-
verted to actual wt % NaCl using the algorithm of Heinrich
et al. (2003) taking into account a contribution of NaCl, KCl,
CaCl2, FeCl2, and MgCl2 to the freezing point depression.
The detection limit was calculated individually for each ele-
ment and is a function of fluid inclusion size and volume of
contained liquid as well as instrument sensitivity. Appendix
1 lists the median, minimum, and maximum values of detec-
tion limits for obtained elements. Gold, Ag, Cu, Se, Te, and
Tl concentrations were less than their detection limits in all
analyzed samples with median detection limits at 1.5, 4.2, 17,
76, and 29 ppm, respectively. Qualitative element composi-
tions of the host mineral were also indirectly obtained during
ablation to intercept fluid inclusions.
Raman spectroscopy
Fluid inclusions were analyzed using a laser Raman micro-
probe based on the Jobin Yvon LabRam-HR800 design with a
high-resolution 800-mm spectrograph and equipped with an
air-cooled 514-nm (green) argon laser set at 50 mW for excita-
tion, at the Fluids Research Laboratory (Virginia Tech). The
goal of the Raman spectroscopy analysis was to test for the
possible presence of CO2 and other gaseous species in fluid
inclusions. The detection limit for CO2 in fluid inclusions is
less than 1 bar. Because CO2 preferentially partitions into
the vapor phase, the vapor bubble was targeted within two-
phase liquid-rich inclusions, and the liquid phase was tested
for fewer inclusions. Two-phase, vapor-rich, and single-phase
vapor-only inclusions were also analyzed.
Fluid Inclusion Petrography and Microthermometry
Fluid inclusions were categorized as primary, pseudosec-
ondary, and secondary based on their time of entrapment
relative to the formation of the host mineral (Roedder, 1984).
Primary inclusions are rare and occur in growth zones (Fig.
4A). Some large isolated inclusions (Fig. 4B) and clusters of
fluid inclusions concentrated in the base part of the quartz
crystals (Fig. 4C), that are not associated with any obvious
fractures, are also considered to be primary, even though
they do not occur in a discrete growth zone (Roedder, 1984).
Secondary fluid inclusions are by far the most common (Fig.
4D-G), and some of these are considered to be pseudosec-
ondary because they occur along healed fractures that termi-
nate within the crystal.
Several fluid inclusion types are identified based on phase
relationships at room temperature and include: (1) two-phase
liquid-rich, (2) two-phase vapor-rich, and (3) single-phase
vapor-only. The deposits examined here all have similar fluid
inclusions types, and therefore these are collectively described
below. Two-phase liquid-rich inclusions with 75 to 90 vol %
liquid are the most common. The cavities occupied by the
fluid are <1 to 60 μm in size, with most less than 30 μm. The
inclusions range from highly irregular to regularly shaped,
with some having negative crystal form. Two-phase vapor-
rich inclusions are rare, and these typically contain more than
90  vol % vapor. Inclusion cavities for vapor-rich inclusions
range in size from <1 to 260 μm and their morphology ranges
from irregular to more commonly well formed with straight
sided walls; some have negative outlines. A number of quartz
veins from the Karangahake, Martha, and Waitekauri deposits
have coexisting liquid- and vapor-rich inclusions (Fig. 4F) that
were most likely trapped under boiling conditions (Bodnar et
al., 1985). Single-phase, vapor-only inclusions also occur at
the Karangahake and Martha deposits (Fig. 4G).
Microthermometric measurements were made on both liq-
uid- and vapor-rich inclusions. However, because the vapor-
rich inclusions contain very little liquid (<10 vol %) it was not
possible to obtain final ice melting temperatures for this inclu-
sion type (cf. Sterner, 1992).
Karangahake
Fluid inclusions were measured in four quartz samples
from the Maria vein (AU 62192, AU 62194, AU 62202, and
AU 62210) and in three quartz samples from the Welcome
vein (AU 62229, AU 62232, and AU 62238). Homogeniza-
tion temperatures for primary, pseudosecondary and sec-
ondary liquid-rich inclusions from the Maria and Welcome
veins overlap and collectively range from 187° to 287°C
(Table 1; Fig. 5A); although individual FIA have narrow Th
ranges. The final ice melting temperature ranges from 0.0° to
−2.3°C, and corresponds to apparent salinities ranging from
~0 to 3.9  wt  % NaCl equiv. Homogenization temperatures
for secondary vapor-rich inclusions range from 225° to 262°C
(Table 1; AU 62210). Assuming hydrostatic conditions, boiling
point with depth curves suggest that the veins formed 270 to
575 m below the former water table (Fig. 6). Whereas coex-
isting liquid- and vapor-rich inclusions are secondary, they do
not record formation conditions of host quartz crystals but
are most likely related to a later boiling stage during the vein
formation.
Martha and Favona (Waihi vein system)
Fluid inclusions were analyzed from samples containing
main-stage quartz (AU 58166), late-stage quartz (AU 58188,
AU 62242), and amethyst (AU 58188, AU 62242) associated
with mineralized samples from the Martha deposit as well as
from late-stage barren quartz from the Favona deposit (AU
59032). Table 1 and Figure 5B provide the summary of micro-
thermometric data.
770 SIMPSON ET AL.

A B

1 mm 200 µm

C D

50 µm

F
200 µm

E 25 µm

50 µm 25 µm

Fig. 4. Fluid inclusion images. A. Quartz crystal with growth zones containing primary fluid inclusions that are further cut
by numerous healed fractures with secondary inclusions, Maria vein level 7, Karangahake deposit (AU 62194). B. Isolated (45
μm) fluid inclusion in quartz of suspected primary origin, Maria vein level 7, Karangahake deposit (AU 62194). C. Abundant
liquid-rich inclusions concentrated in the core of a prismatic quartz crystal and possibly of primary origin, Martha deposit
(AU 58166). D. Pseudosecondary liquid-rich inclusion in quartz, Martha deposit (AU 58166). E. Trail of secondary liquid-rich
inclusions in healed fractures in quartz, Sovereign (AU 59743). F. Coexisting liquid-rich inclusions with a vapor-rich inclusion
indicative of boiling conditions, quartz, Favona deposit (AU 59032). G. A fluid inclusion assemblage with vapor-only inclu-
sions in quartz, Maria vein level 8, Karangahake deposit (AU 62202).

Due to the lack of large primary fluid inclusions in quartz
and amethyst from the Martha deposit, the microthermo-
metric and LA-ICP-MS studies were performed only on
pseudosecondary and secondary inclusions. Liquid-rich
pseudosecondary inclusions in quartz have apparent salini-
ties less than 1.7 wt % NaCl equiv and homogenize between
181° and 241°C. In some places (e.g., AU 58166), liquid-
rich inclusions coexist with vapor-rich inclusions, and these
two different inclusion types have similar homogenization
temperatures, indicating entrapment from a boiling fluid.
Assuming hydrostatic conditions, fluid inclusions were
entrapped at depths between 200 and 400 m below the
former water table (Fig. 6). Secondary inclusions are more
saline, ranging from 1.4 to 3.7  wt  % NaCl equiv and have
Th values of 202° to 241°C. Pseudosecondary inclusions in
amethyst have salinities around 4.0  wt  % NaCl equiv and
homogenization temperatures between 218° and 241°C.
Secondary inclusions are slightly more dilute (3.2−4.2 wt %
NaCl equiv.) with homogenization temperatures between
213° and 242°C.
The single quartz crystal studied from the Favona deposit is
from a cavity lined by elongated quartz crystals that overgrew
 ADULARIA-SERICITE EPITHERMAL Au-Ag DEPOSITS, S. HAURAKI GOLDFIELD 771

A Karangahake
60 5.0

Primary
Number of fluid inclusions

Salinity (wt % NaCl equiv)

4.0
Pseudosecondary
40 Secondary
3.0

2.0
20

1.0

0 0.0
100 150 200 250 300 100 150 200 250 300
Temperature of homogenization (°C) Temperature of homogenization (°C)

B Martha & Favona

90 5.0

Primary
Number of fluid inclusions

Pseudosecondary Salinity (wt % NaCl equiv) 4.0

60 Secondary
3.0

2.0
30

1.0

0 0.0
100 150 200 250 300 100 150 200 250 300
Temperature of homogenization (°C) Temperature of homogenization (°C)

C Waitekauri
30 5.0

Primary
Number of fluid inclusions

Salinity (wt % NaCl equiv)

Pseudosecondary 4.0

20 Secondary
3.0

2.0
10

1.0

0 0.0
100 150 200 250 300 100 150 200 250 300
Temperature of homogenization (°C) Temperature of homogenization (°C)

Fig. 5. Fluid inclusion Th vs. frequency and Th vs. salinity plots for the (A) Karangahake, (B) Martha plus Favona, and
(C) Waitekauri deposits. The Th vs. frequency plots are composites of all measurements with values for primary, pseudosec-
ondary, and secondary inclusions differentiated. The colored areas represent interquartile ranges (values between 1st and 3rd
quartile) and the bars show intervals between the minimal and maximal recorded values.
 Table 1. Summary of Fluid Inclusion Results for Samples from the Karangahake, Martha, Favona, and Waitekauri Deposits
772
Sample1 Vein Level (m asl) Mineral Type FIA Th range no. Avg Tm range no. Avg Salinity2 Comments TNa/K3

Karangahake
62192 Maria Level 6 (Talisman) Quartz P FIA_1 198–236 16 217 –0.5 to –0.6   5 –0.6 0.9–1.1
S FIA_2 233–247   8 243 –0.6 to –0.7   4 –0.6 1.1–1.2
S (PS?) FIA_3 230–250 18 237 –0.4 to –0.6 12 –0.5 0.7–1.1 339

62194 Maria Level 7 (Talisman) Quartz PS FIA_1 187–270 30 232 –0.1 to –2.3 17 –0.8 0.2–3.9 173
P FIA_2 228–238   4 235 –1.6 to –1.8   3 –1.7 2.7–3.1
P FIA_3 233–263 22 245 –0.4 to –0.6   6 –0.5 0.7–1.1

62202 Maria Level 8 (Talisman) Quartz S FIA_1 212–246 16 230 0.0 to –0.4 10 –0.1 0.0–0.7 241–272
S (PS?) FIA_2 222–235 10 230 –0.3 to –0.5   7 –0.4 0.5–0.9 272–331
S FIA_3 215–230  4 221 –0.3  2 –0.3 0.5
S FIA_4 228–257 12 237 –0.4 to –0.6   6 –0.5 0.7–1.1 367

62210 Maria (BM-37) Level 8 (Talisman) Quartz S (PS?) FIA_1 211–251 22 233 –0.3 to –1.4 13 –1.1 0.5–2.4 264–323
S FIA_2 212–283 13 239 0.0 to –1.8 13 –0.7 0.0–3.1 Liquid-rich
FIA_2 225–262  5 244 - - - - Vapor-rich

62229 Welcome Level 8/(5A; Crown) Quartz PS FIA_1 209–216 15 211 –0.8 to –0.9   5 –0.8 1.4–1.6
S FIA_2 215–220   5 217 –1.0 to –1.1   3 –1.1 1.7–1.9
PS FIA_3 202–244 19 235 –0.4 to –0.8   7 –0.6 0.7–1.4

62232 Welcome Level 8/(5A; Crown) Quartz PS FIA_1 242–282 12 259 –0.2 to –0.7   8 –0.6 0.4–1.2
P FIA_2 249–287 13 265 –0.1  4 –0.1 0.2
S (PS?) FIA_3 213–227 21 223 –0.4 to –0.5 11 –0.4 0.7–0.9 212
S FIA_4 215–228  9 223 –0.4  2  0.7 0.7

62238 Welcome Level 11 (Crown) Quartz S FIA_1 212–261 30 238 0.0 to –1.2 14 –0.4 0.0–2.4 252–345
SIMPSON ET AL.

PS FIA_2 199–234 20 224 –0.4 to –0.6   8 –0.6 0.7–1.1

Martha
58166 Open pit –72.5 m asl/927.5 m RL Quartz PS FIA_1 181–228 19 206 0.0 to –0.4 10 –0.2 0.0–0.7 Liquid-rich 256–292
FIA_1 205–243  7 224 - - - - Vapor-rich
PS FIA_2 202–241 19 223 –0.3 to –1.0 10 –0.5 0.5–1.7 244–333
PS FIA_3 200–238 16 215 –0.1 to –0.3 11 –0.2 0.2–0.5 285–331
PS FIA_4 222–225 28 223 –0.8 to –1.0 13 –0.9 1.4–1.7 323–370

58188 Open pit –55 m asl/945 m RL Amethyst S FIA_1 213–242   9 229 –2.0 to –2.4   9 –2.1 3.4–4.0
S FIA_2 215–236   7 225 –2.1 to –2.3   6 –2.2 3.5–3.9 208
Quartz S FIA_3 206–222   6 214 –0.8 to –1.8   6 –1.6 1.4–3.1 273–309
S FIA_4 224–241  3 235 –1.6  3 –1.6 2.7 243 

62242 Level 14 –400 m asl/600 m RL Amethyst S FIA_1 217–231 22 223 –1.9 to –2.5   6 –2.2 3.2–4.2
–400 m asl/600 m RL PS FIA_2 218–241 15 226 –2.3 to –2.4   4 –2.4 3.9–4.0 288–310
Quartz S FIA_3 202–230 10 216 –1.7 to –2.2   7 –2 2.9–3.7 279–299

Favona
59032 Underground –125 m asl/945 m RL Quartz S (PS?) FIA_1 215–242 22 231 0.0 10   0.0 0.0
S (PS?) FIA_2 213–250 23 226 0.0 to –0.4   8 –0.3 0.0–0.7
S (PS?) FIA_3 217–239 22 229 0.0 to –0.4 11 –0.3 0.0–0.7 278
PS FIA_4 227–251 10 240 –0.2 to –0.8   5 –0.4 0.4–1.4
 ADULARIA-SERICITE EPITHERMAL Au-Ag DEPOSITS, S. HAURAKI GOLDFIELD 773

213–279

158–327
Salinity2 Comments TNa/K3

335

258
200

Martha
Jubilee

Liquid-rich
Scotia

Karangahake
Vapor-rich

Notes: FIA = fluid inclusion assemblage. FIA numbers are arbitrarily assigned and do not reflect paragenetic sequence; P = primary, PS = pseudosecondary, S = secondary, - = no data
400

Depth / m
0.0

0.5–1.1
600
0.0–0.5
0.7–1.1

0.5–1.2

0.0–0.9
-
0.9

0.9
0.9

0.2
0.2
800
10 % NaCl
5 % NaCl
0 % NaCl
1000
–0.5

0.0  9  0.0

–0.5
–0.5

–0.1
–0.1

–0.2
–0.5

–0.6

–0.1

–0.4
Avg

100 150 200 250 300

Temperature / °C
Fig. 6. Fluid inclusion homogenization temperatures for coexisting liq-
–0.5  1

–0.5  1
–0.5  1

–0.1  8
–0.1  3

0.0 to –0.5  6
no.

–0.4 to –0.6   7

–0.3 to –0.7   8

0.0 to –0.3   9

–0.3 to –0.6   3
-

uid- and vapor-rich inclusions plotted on the boiling point-depth curves for
fluids of different salinities (Haas, 1971). The formation depths have been
estimated assuming a hydrostatic pressure gradient.
Tm range

porous cryptocrystalline quartz with casts of parallel aligned

platy calcite (Fig. 3G). Three secondary and one pseudosec-
ondary FIAs have overlapping Th ranges of 213° to 251°C,
261

250

226

228
Avg

249

242

227

227

and salinity values of up to 1.4 wt % NaCl equiv (Table 1; Fig.

-
-

-
-

5B).
Waitekauri
257–265  4

18

215–236  4

216–246  8
no.

12

17

18

12
-
-

-
-
Table 1. (Cont.)

Fluid inclusions were measured in quartz veins from the

Waitekauri deposits and prospects (Simpson and Mauk
Th range

244–257
227–262

236–248

210–243

225–230

2011). Because most of the old mine workings are inacces-

-
-

-
-

sible, the quartz vein material was limited to small veins

intercepted in drill holes that selectively targeted areas adja-
cent to old workings (Fig. 2E). Most quartz veins are from
FIA_2

FIA_1

FIA_2
FIA_3

FIA_1
FIA_2
FIA_3

FIA_1
FIA_1

FIA_1

FIA_1

FIA_2

the Sovereign deposit (AU 59733, AU 59741, and AU 59743)

FIA

but also included is a single vein from an area between Jubi-

lee and Scotia (AU 59871) and a single vein from Scotia
(AU 59907).
Type

PS
PS

PS
P

P
S

S
S

P
S

Homogenization temperatures for primary, pseudosecond-

ary, and secondary liquid-rich inclusions in quartz from the
Sovereign deposit overlap and range from 227° and 265°C
Mineral

Quartz

Quartz
Quartz

Quartz

Quartz

1 AU# = the University of Auckland sample collection number

and have apparent salinities of up to 1.2 wt % NaCl equiv.

Na/K = geothermometer after Verma and Santoyo (1997)

Quartz from Scotia is characterized by slightly cooler (Th =

216°−246°C) and lower salinity fluids with less than 1.1  wt

% NaCl equiv (Table 1; Fig. 5C). Pseudosecondary liquid-
rich inclusions in a thin quartz vein that occurs between the
Jubilee and Scotia deposits (Sample AU 59871) homogenize
between 210° and 243°C and have less than 0.5 wt % NaCl
Level (m asl)

2 Salinity = wt % equival (Bodnar, 1993)

equiv (Table 1; Fig. 5C). These inclusions coexist with vapor-

208

Scotia  37
131

147

134

rich inclusions and reflect the temperature of trapping and a

formation depth under hydrostatic conditions of 300 m below
the former water table (Fig. 6; Haas, 1971).
Jubilee-Scotia

Fluid Inclusion Compositions

Sovereign
Sovereign

Sovereign

Microanalyses by LA-ICP-MS were carried out on 153

individual inclusions. Relatively large inclusions (>10 μm)
Vein

were targeted because of lower detection limits due to larger

Waitekauri

amounts of contained liquid (e.g., Heinrich et al., 2003). A

Sample1

59741

59907

number of vapor-rich and vapor-only inclusions were also

59733

59743

59871

3T

analyzed but because these contained insignificant amounts

774 SIMPSON ET AL.

of liquid, no transient signal was observed. Accordingly, we
report only values from liquid-rich inclusions. Several ablated
inclusions have Tm values of 0.0°C but showed a transient
signal response for Na and rarely other elements. For these
inclusions, a Tm value of −0.1°C was used as a proxy for their
bulk salinity. Appendix 1 details the composition of individual
fluid inclusions.
Fluid inclusions from all three localities contain measurable
concentrations of Na and commonly contain measureable
concentrations of Sb, K, As, Ca, Sr, Rb, and Ba. Concentra-
Where detected, K concentrations typically exceed Ca
concentrations (Fig. 7), but some inclusions are relatively
enriched in Ca (App. 1). Measured Sb concentrations range
from 16 to 2,167 ppm, although calculation of the concen-
tration in the fluid is complicated by the common occur-
rence of Sb in the quartz host. For inclusions in Sb-free
A gas blank quartz FI
10 07

tions of the other elements (Ag, Al, Au, Cu, Fe, Li, Mg, Mn,
106
Pb, Se, Te, Ti, Tl, and Zn) are typically at or below the limit of Si
detection, although fluid inclusions from the Waitekauri area 10 5

contain Li and Al that exceed detection limits in 11% of the

Intensity (cps)
measured inclusions. However, the measured Al concentra- 104 K
tions of several tens to hundreds ppm (App. 1) are unusually Na
high for near-neutral hydrothermal fluids and we assume that 10 3

Ca
the recorded Al signals may reflect an accidentally captured
mineral phase rather than fluid itself. 10 2

Sb
Qualitative element abundances in the host mineral were
also indirectly obtained during ablation to intercept fluid 10 1

inclusions. Many of the quartz crystals contain variable

100
amounts of Sb (Fig. 7), and some contain Al that is commonly 0 60 120 180 240 300 360
coupled with Li. Amethyst has variable amounts of Fe, Mn, Time (seconds)
and Sb (Fig. 7).
Antimony commonly occurs in both the trapped inclusion B gas blank quartz FI
and in the host mineral. Figure 7 shows LA-ICP-MS tran-
10 07

sient profiles with Sb in the matrix of quartz and amethyst as

shown by its parallel trace with Si. Upon breach of the inclu-
106
sion, signified by a sharp rise in Na, there is a concomitant Si
increase in Sb indicating that this element is also present in 10
5

the inclusion and in greater concentrations than in the enclos-

Intensity (cps)

ing quartz matrix. 104 K

Na
Karangahake 103
Fluid inclusions hosted in quartz from both the Maria and Sb
Welcome veins contain concentrations of Na, Sb, K, As, Ca, 102
As
and Sr that exceed the detection limits in 100, 69, 33, 25, 22,
101
and 9% of the inclusions, respectively (Fig 8; App. 1). Other
elements (Ag, Al, Au, Ba, Cu, Fe, Li, Mg, Mn, Pb, Rb, Se,
100
Te, Ti, Tl, and Zn) have concentrations that are less than their 0 60 120 180 240 300 360
respective detection limits in 98 to 100% of the samples. Time (seconds)
Sodium and Sb have median concentrations of 3,434 and 271
ppm, respectively. Median values were not calculated for the C gas blank amethyst FI
other elements detected because these occur in only a few
1007
inclusions and in variable concentrations.
106

Fig. 7. LA-ICP-MS transient signal profiles for inclusions in quartz and 105 Si
Intensity (cps)

amethyst. A. Quartz-hosted fluid inclusion with breach at 223 s as indicated

by the sharp rise in Na paralleled by K, Ca, and Sb (AU 62194, Maria vein 104 K
level 6, Karangahake deposit). B. Fluid inclusion in quartz with Na, K, Sb,
and As. Antimony is incorporated in quartz as seen by a parallel rise of this Na
103
element with Si, but also clearly occurs in the inclusion liquid as seen by its Ca
paralleled rise with Na on breach (AU 58166, Martha deposit). C. Amethyst
102 Sb
with Fe and significant amounts of Sb in the host. The inclusion liquid has
Fe
Na, K, Ca, and also some Sb (AU 58188, Martha deposit). Steps in the Si
concentration relate to increasing beam diameter resulting in the ablation 101

of greater area of the mineral and consequent increase in counts (concen-

tration). Changing diameter initially requires blocking the laser resulting in 100
decreasing counts prior to the rise. The diameter is set to encompass the 0 60 120 180 240 300 360 420

whole inclusion when ablated. Time (seconds)

 ADULARIA-SERICITE EPITHERMAL Au-Ag DEPOSITS, S. HAURAKI GOLDFIELD 775

A B C
2,500 1,000 2,500

2,000 800 2,000

Ca (ppm)

Sb (ppm)
1,500 600 1,500
K (ppm)

1,000 400 1,000

500 200 500

0 0 0
0 2,000 4,000 6,000 8,000 10,000 0 2,000 4,000 6,000 8,000 10,000 0 2,000 4,000 6,000 8,000 10,000
Na (ppm) Na (ppm) Na (ppm)

D E Maria vein Welcome vein

500 500
AU#62192 AU#62229
AU#62194 AU#62232
400 400
AU#62202 AU#62238
AU#62210
As (ppm)

As (ppm)

300 300

200 200

100 100

0 0
0 2,000 4,000 6,000 8,000 10,000 0 500 1,000 1,500 2,000 2,500
Na (ppm) Sb (ppm)

F G H
5,000 2,500 5,000

4,000 2,000 4,000

Ca (ppm)

Sb (ppm)
3,000 1,500 3,000
K (ppm)

2,000 1,000 2,000

1,000 500 1,000

0 0 0
0 3,000 6,000 9,000 12,000 15,000 0 3,000 6,000 9,000 12,000 15,000 0 3,000 6,000 9,000 12,000 15,000
Na (ppm) Na (ppm) Na (ppm)

I J Martha Favona
500 500
AU#58166 AU#59032
AU#58188
400 400
AU#62242
As (ppm)

As (ppm)

300 300

200 200

100 100

0 0
0 3,000 6,000 9,000 12,000 15,000 0 1,000 2,000 3,000 4,000 5,000
Na (ppm) Sb (ppm)

Fig. 8. LA-ICP-MS element plots for: The Karangahake deposit: A. Na vs. K. B. Na vs. Ca. C. Na vs. Sb. D. Na vs. As.
K E. Sb vs. As. The Martha and Favona deposits:
L F. Na vs. K. G. Na vs. Ca. H. Na vs. Sb. I. NaM
vs. As. J. Sb vs. As. The Waitekauri
1,000 deposits: K. Na vs. K. L. Na vs. Ca. M. Na500vs. Sb. N. Na vs. As. O. Sb vs As. 500

800 400 400

quartz, the trapped fluid contains 16 to 988 ppm Sb (n = ppm), and As concentrations do not correlate with Na con-
9). Arsenic
600 occurs in a lesser number of fluid 300 inclusions in tents (Fig. 8D). 300
Ca (ppm)

Sb (ppm)
K (ppm)

concentrations from 61 to 406 ppm; it is not incorporated

400
into the quartz, and As concentrations covary with Sb (Fig.
200
Martha and Favona (Waihi 200
vein system)
8E).200Although our data are limited, the range 100 of As values Fluid inclusions from the Martha and Favona deposits con-
100

for inclusions from the Maria vein (61−406 ppm) is slightly tain concentrations of Na, Sb, K, As, Ca, Sr, Rb, and Ba that
0 0 0
greater 0than1,000
in inclusions
2,000 from4,000the Welcome
3,000 5,000 vein
0 (63−147
1,000 2,000 exceed
3,000 their
4,000 detection
5,000 limits
0 in1,000
100, 2,000
75, 70, 42, 34,
3,000 4,000 34, 21,
5,000
Na (ppm) Na (ppm) Na (ppm)

N O Sovereign Jubilee-Scotia Scotia

50 50
AU#59741 AU#59871 AU#59907
AU#59743
40 40
AU#59733
 100 100

0 0
0 3,000 6,000 9,000 12,000 15,000 0 1,000 2,000 3,000 4,000 5,000
Na (ppm) Sb (ppm)
776 SIMPSON ET AL.

K L M
1,000 500 500

800 400 400

600 300 300

Ca (ppm)

Sb (ppm)
K (ppm)

400 200 200

200 100 100

0 0 0
0 1,000 2,000 3,000 4,000 5,000 0 1,000 2,000 3,000 4,000 5,000 0 1,000 2,000 3,000 4,000 5,000
Na (ppm) Na (ppm) Na (ppm)

N O Sovereign Jubilee-Scotia Scotia

50 50
AU#59741 AU#59871 AU#59907
AU#59743
40 40
AU#59733
As (ppm)

As (ppm)

30 30

20 20

10 10

0 0
0 1,000 2,000 3,000 4,000 5,000 0 50 100 150 200 250
Na (ppm) Sb (ppm)

Fig. 8. (Cont.)

and 8% of the inclusions, respectively (Fig. 8; App. 1). Other
elements (Ag, Al, Au, Cu, Fe, Li, Mg, Mn, Pb, Se, Te, Ti, Tl,
and Zn) have concentrations that are less than their respec-
tive detection limits in 96 to 100% of the samples. Sodium,
Sb, and K have median concentrations of 2,665, 245, and
586 ppm, respectively. Median values were not calculated for
the other elements because only a few inclusions show these
elements and they occur in varying amounts.
Waitekauri
Fluid inclusions from the Waitekauri area contain Na, K, Ca,
Sr, Sb, As, Ba, Li, and Al, which occur in concentrations that
exceed their detection limits in 100, 53, 53, 33, 22, 16, 13, 11,
and 11% of the inclusions, respectively (Fig. 8; App. 1). Other
elements (Ag, Au, Cu, Fe, Mg, Mn, Pb, Rb, Se, Te, Ti, Tl,
and Zn) have concentrations that are less than their respective
detection limits in 96 to 100% of the samples. Sodium, K, and
Ca have median concentrations of 1,000, 148, and 36  ppm,
respectively. Median values cannot be calculated for the other
elements because these occur in only a few inclusions and in
variable concentrations.
Raman Spectroscopy
Primary, pseudosecondary, and secondary fluid inclusions
from all investigated deposits were analyzed by Raman spec-
troscopy. Except for water, all other volatiles, including CO2,
were less than their detection limits in liquid-rich as well as
in coexisting vapor-rich inclusions. Traces of CO2 have been
detected only in vapor-rich and vapor-only inclusions that
occur independently of adjacent liquid-rich inclusions in a
single sample from the Karangahake deposit (AU 62232; Wel-
come vein). Because CO2 was not detected in coexisting liq-
uid- and vapor-rich inclusions, the boiling point with depth
curves shown in Figure 6 were calculated for the CO2-free
system (see Bodnar et al., 1985)
Discussion
The mineralized quartz veins from the adularia-sericite epi-
thermal Au-Ag deposits of the southern Hauraki goldfield are
characterized by cryptocrystalline and very fine grained quartz
bands that are interbanded with coarse-grained quartz and
amethyst. The ore mineralization occurs only in cryptocrys-
talline to very fine grained quartz that lacks large fluid inclu-
sions, as is typical of this deposit type (Bodnar et al., 1985).
Therefore, fluid inclusion data from coarse-grained quartz
and amethyst bands may not represent the ore-forming con-
ditions, even though they are part of the overall hydrothermal
system that deposited the gold and silver.
Modern geothermal systems are considered to be the active
analogue of adularia-sericite epithermal deposits (Henley and
Ellis, 1983). Generally, adularia-sericite epithermal deposits
form in shallow hydrothermal systems where surficial waters
mix with deeper, heated alkali chloride waters in an upwelling
or lateral flow regime, high above or offset from a heat source
at depth (Heald et al., 1987). Oxygen and hydrogen isotope
analyses show that these chloride waters are predominantly
meteoric (Craig, 1963), but they commonly include a compo-
nent of magmatic water (Giggenbach, 1992). Concentrations
of the main aqueous constituents in chloride waters (i.e., Na,
K, Ca, Si) reflect water-rock interactions and represent equi-
librium with quartz, albite, adularia, illite, chlorite, pyrite, and
calcite, which form as secondary minerals during alteration
of igneous rocks (Giggenbach, 1997). The volatile content is
dominated by CO2, with H2S generally the next most abun-
dant gas. The total gas content affects vapor pressure and the
depth of boiling (Bodnar et al., 1985; Hedenquist and Henley,
 ADULARIA-SERICITE EPITHERMAL Au-Ag DEPOSITS, S. HAURAKI GOLDFIELD 777
1985). Boiling results in loss of CO2 and H2S from the liquid
into the vapor and the gases rise to the surface along a path
distinct from the residual liquid. These gases can be partially
absorbed into shallow groundwaters with oxidation of H2S to
H2SO4 in the vadose zone, forming steam heated acid-sulfate
waters (~1,000 ppm SO4), and the condensation of CO2,
forming steam heated CO2-rich waters (>1 wt %; Henley and
Ellis, 1983; Hedenquist, 1990). Both acid-sulfate and CO2-
rich waters can mix with chloride waters to generate hybrid
compositions. The hydrologic structure of a geothermal field
is strongly influenced by topographic relief, which controls
the geometry and lateral flow of chloride waters (<0.5−>5 km)
near the surface and the distribution of steam heated acid-sul-
fate and CO2 waters that occur peripheral to the main upflow
(Henley and Ellis, 1983; Hedenquist and Lowenstern, 1994).
Data from modern geothermal systems (Ellis, 1970; Henley
and Ellis, 1983; Hedenquist, 1990; Joseph et al., 2011; Rae
et al., 2011; Scott et al., 2014) and numerous thermodynamic
studies (e.g., Drummond and Ohmoto, 1985; Spycher and
Reed, 1989; Heinrich, 2005) show that epithermal deposits
are related to boiling conditions. Furthermore, fluid inclu-
sion studies show that coexisting two-phase liquid- and vapor-
rich inclusions are common, indicating trapping of boiling
fluids (Bodnar et al., 1985; Simmons et al., 2005; Moncada
et al., 2012). Our study similarly documents the coexistence
of liquid- and vapor-rich inclusions in pseudosecondary (AU
58166, AU 59871) and secondary fluid inclusion assemblages
(AU 62210) hosted by coarse-grained quartz. In epithermal
environments, gold is most likely transported as a bisulfide
complex (Berger and Henley, 1989; Heinrich et al., 1999;
Steffanson and Seward, 2003, 2004; Williams-Jones and Hein-
rich, 2005; Seward et al., 2014). Boiling contributes to H2S
degassing and decreases gold solubility. Adiabatic boiling,
which results in separation of the vapor phase and simulta-
neous cooling of the liquid phase, has been recognized as a
particularly effective mechanism for gold deposition (Seward,
1989). Solubility of gold is controlled by pH and redox poten-
tial of mineralizing fluids as well (Brown, 1986; Stefansson
and Seward, 2003, 2004; Moncada and Bodnar, 2012; Seward
et al., 2014).
The deep reservoir fluid temperature can be estimated
from Na and K concentrations obtained by LA-ICP-MS anal-
yses of individual fluid inclusions. Table 1 provides tempera-
tures calculated from the Verma and Santoyo (1997) Na/K
geothermometer. Coexisting vapor- and liquid-rich inclusions
reflect boiling conditions, and therefore their homogenization
temperatures were used for the calculation of the steam loss
assuming an adiabatic system (e.g., Henley, 1984):
HL,T(Na/K) =
(1 − y) × HL,Th(V-rich FIAs) + y × HV,Th(V-rich FIAs). (1)
In this equation, HL,T(Na/K) represents a specific enthalpy of
the deep reservoir fluid at the temperature estimated from
the Na/K geothermometer, HL,Th(V-rich FIAs) and HV,Th(V-rich FIAs)
are specific enthalpies of liquid and vapor phases separated
during boiling at a temperature equal to the homogenization
temperature of vapor-rich inclusions coexisting with liquid-
rich inclusions, and y is the steam (vapor) fraction. The spe-
cific enthalpies for liquid and vapor phases (assuming pure
H2O) were adopted from Keenan et al. (1969).
The calculated steam loss in the Karangahake deposit
(Maria vein, AU 62210) ranges between 8 and 17%, between
15 and 23% in the Martha deposit (AU 58166), and between
13 and 18% in the Waitekauri (AU 59871) deposit. Nonvolatile
components, such as Na+, K+, Ca2+, Cl−, H4SiO4, are assumed
to have remained in the liquid phase during boiling, whereas
volatile components including H2S preferentially partitioned
into the vapor phase. Figures 9 and 10 display differences in
gold and SiO2 solubilities as functions of the temperature and
pH during the isothermal boiling, conductive cooling, and
adiabatic boiling. The solubility diagrams are constructed for
the Karangahake, Martha, and Waitekauri deposits assum-
ing a relatively reducing environment (the predomination of
H2S over SO42–) and applying the calculated steam loss frac-
tions and the thermodynamic data published by Helgeson et
al. (1978), Wagman et al. (1982), Sverjensky (1997), and the
SUPCRT model and database (Johnson et al., 1992). The gas
distribution coefficient (B) for H2S was adopted from Giggen-
bach (1980):
log BH2S = 4.0547 − 0.00981 × t(°C). (2)
Neutral to alkaline fluids have better capability for gold
transport than acid fluids (Fig. 9), and adiabatic boiling is
a more effective Au deposition mechanism than conduc-
tive cooling and isothermal boiling (Fig. 10). Furthermore,
adiabatic boiling has a significant influence on deposition of
different SiO2 forms, resulting in alternation of quartz depo-
sition (no boiling or weak boiling) with chalcedony and cris-
tobalite deposition (more effective adiabatic boiling) within
epithermal veins (Fig. 10). Episodic fluid fluxes accompanied
by local brecciation of earlier formed SiO2 bands contributed
to the complex quartz vein textures observed (Skinner and
Mauk, 2013). The presence of single-phase vapor-only fluid
inclusions in some of mineralized samples most likely reflects
local flashing, which is an effective mechanism of Au and Ag
deposition in epithermal deposits (Brown, 1986; Moncada
et al., 2012). Flashing also results in the deposition of amor-
phous silica with a colloform texture and does not result in
trapping of measurable primary fluid inclusions, although sec-
ondary fluid inclusion assemblages containing single-phase
vapor-only (or vapor-rich) inclusions may be trapped in ear-
lier formed quartz in the vein (Moncada et al., 2012). Flash-
ing presumably results from an instantaneous fluid pressure
decrease to a value less than hydrostatic pressure, which con-
verts essentially 100% of the original liquid into a vapor phase
(Brown, 1986; Moncada et al., 2012).
Table 2 lists representative chemical compositions of deep
reservoir chloride waters for a selection of geothermal fields
from around the world. Their Na concentrations mostly range
between ~435 and 9,130 ppm, although greater Na contents
have been reported for several geothermal fields including
Fushime, Japan (Okada et al., 2000), Ladolam, Papua New
Guinea (Simmons and Brown, 2006), and Salton Sea, United
States (Lippmann et al., 1999).
Notwithstanding the issue of CO2 quantification and its
effect on LA-ICP-MS absolute concentrations, the Na content
of the inclusions from Karangahake (~260−10,200 ppm), Mar-
tha and Favona (~440−9,600 ppm quartz; ~9,680−13,700 ppm
amethyst), and Waitekauri (~320−3,700 ppm) have higher dis-
solved salt concentrations than chloride waters from geothermal
778 SIMPSON ET AL.

Karangahake Deep reservoir (initial) fluid (T0=287°C; c(HS )0=10

- -9.1
mol/L) Conductive cooling
Isothermal boiling
(8% steam lost; 70% H2S lost)
Adiabatic boiling
(17% steam lost; 92% H2S lost)

-9 -8 -7
0.1 ppb Au 1 ppb Au 10 ppb Au
Au / log mol/L

-10 -9 -8
0.01 ppb Au 0.1 ppb Au 1 ppb Au

pH=4.6 pH=5.6 pH=6.6

(acid) (neutral) (alkaline)
-11 -10 -9
225 245 265 285 225 245 265 285 225 245 265 285
Temperature / °C Temperature / °C Temperature / °C
A

Martha Deep reservoir (initial) fluid (T0=295°C; c(HS )0=10

- -9.1
mol/L) Conductive cooling
Isothermal boiling
(15% steam lost; 87% H2S lost)
Adiabatic boiling
(23% steam lost; 96% H2S lost)

-9 -8 -7
0.1 ppb Au 1 ppb Au 10 ppb Au
Au / log mol/L

-10 -9 -8
0.01 ppb Au 0.1 ppb Au 1 ppb Au

-11 -10 -9
0.001 ppb Au pH=4.6 0.01 ppb Au pH=5.6 pH=6.6
0.1 ppb Au
(acid) (neutral) (alkaline)
205 225 245 265 285 205 225 245 265 285 205 225 245 265 285
B Temperature / °C Temperature / °C Temperature / °C

Waitekauri Deep reservoir (initial) fluid (T0=283°C; c(HS )0=10

- -9.1
mol/L) Conductive cooling
Isothermal boiling
(13% steam lost; 88% H2S lost)
Adiabatic boiling
(18% steam lost; 94% H2S lost)

-9 -8 -7
0.1 ppb Au 1 ppb Au 10 ppb Au
Au / log mol/L

-10 -9 -8
0.01 ppb Au 0.1 ppb Au 1 ppb Au

-11 -10 -9
0.001 ppb Au pH=4.6 0.01 ppb Au pH=5.6 0.1 ppb Au pH=6.6
(acid) (neutral) (alkaline)
215 235 255 275 295 215 235 255 275 295 215 235 255 275 295
C Temperature / °C Temperature / °C Temperature / °C

Fig. 9. The solubility of Au as a function of temperature, pH, and reaction path (conductive cooling, isothermal boiling,
and adiabatic boiling). Temperature of the deep reservoir (initial) fluids for each studied deposit was calculated from the Na/K
geothermometer proposed by Verma and Santoyo (1997). The initial sulfur activity is estimated as an average value between
low S fugacity (pyrite-pyrrhotite buffer) and high S fugacity (chalcopyrite-pyrite-bornite buffer) in a pH neutral environment
at the temperature estimated for deep reservoir fluids. The degree of steam and H2S lost is calculated from the deep reservoir
fluid temperature and homogenization temperatures of cogenetic vapor- and liquid-rich inclusions.

fields of the nearby Taupo volcanic zone, New Zealand, (e.g., Mahon, 1977) and the geothermal fields hosted in andesite
Ohaaki, ~400−1,450 ppm, median 990  ppm; Hedenquist, and underlying diorite such as the Greater Tongonan geother-
1990), most of those in Japan (e.g., Ogiri, ~400−850 ppm, mal field, which has two distinct and separate upflow zones
median 470 ppm; Goko, 2000) and many others from around at Mahio and Mahanamagdong. The sodium content of geo-
the world (e.g., Olkaria, ~350−950 ppm; Omenda, 1998). Our thermal fluids from Mahio ranges from ~2,600 to 9,130 ppm
fluid inclusion data show Na concentrations comparable to (avg 6,000 ppm), whereas fluids from Mahanamagdong aver-
those in chloride waters from the geothermal fields associ- age ~2,300 ppm (Lovelock et al., 1982). Chloride waters from
ated with andesite volcanoes (e.g., Palinpinon, ~1,400−4,000 Mahio are enriched in 18O (δ18O ≈ 0‰) and 2H (δD H −33‰)
ppm; Rae et al., 2011; El Tatio, ~1,900−5,000 ppm; Ellis and and are interpreted as a mixture of meteoric water with up to
 ADULARIA-SERICITE EPITHERMAL Au-Ag DEPOSITS, S. HAURAKI GOLDFIELD 779

isothermal boiling
adi
-1.50 aba
tic
boi
ling
cooling Amorphous silica
Cristobalite beta

Concentration of SiO2 (aq ) / log mol/L

-1.75
Cristobalite alpha

Chalcedony

Quartz
-2.00

-2.25

Karangahake Martha Waitekauri

reservoir fluid, 287°C reservoir fluid, 295°C reservoir fluid, 283°C
8% steam lost, 262°C 15% steam lost, 243°C 13% steam lost, 236°C
17% steam lost, 225°C 23% steam lost, 205°C 18% steam lost, 215°C
-2.50
200 210 220 230 240 250 260 270 280 290 300
Temperature / °C
Fig. 10. The solubility of SiO2 and deposition of different SiO2 forms as a function of temperature, and reaction path
(conductive cooling, isothermal boiling, and adiabatic boiling). Initial SiO2 concentration is estimated from the SiO2 geother-
mometer published by Fournier and Potter (1982). The solubility curves for different SiO2 forms were constructed after the
thermodynamic data published by Helgeson et al. (1978).

40% magmatic water. It is inferred that Mahanamagdong has Ca. An exception is the deep reservoir fluids from the Salton
the same source fluid but is more diluted (Alvis-Isidro et al., Sea where Ca > K, but these fluids are exceptionally saline
1993). Previous fluid inclusion and oxygen isotope analyses of (Na 54,800 ppm, Ca 28,500 ppm, and K 17,700 ppm) and
vein quartz, amethyst, and calcite from the Martha deposit are derived from dissolution of surface and buried lacustrine
demonstrate that at the southern Hauraki goldfield deep flu- evaporites, as well as incorporation of fossil lake waters pro-
ids (δ18Owater = +0.6‰) were mixed with heated (160°–180°C) duced by evaporation (McKibben et al., 1987; Lippmann et
groundwater of local meteoric water composition (–5.5‰; al., 1999). Although restricted to few examples, the signifi-
Brathwaite and Faure, 2002). cance of inclusions with Ca > K is not known.
Although not shown in Table 2, there can be considerable Table 3 shows the concentrations of trace metalloids and
variation in fluid composition across a geothermal field, and metals for deep reservoir chloride waters in several New Zea-
this is more apparent for reservoirs with higher Cl− content. land geothermal fields and the Palinpinon field. Antimony con-
For example, at Palinpinon, the calculated reservoir chlo- centrations range from 0.04 to 2.08 ppm, and As from 0.17 to
ride waters have 2,077 to 5,260 ppm Cl− and the parent fluid 4.86 ppm, with As occurring in greater concentration than Sb,
contains approximately 4,050 ppm Cl−. Chloride waters with except at Ngawha, where Sb exceeds As (Brown and Simmons,
greater amounts of Cl− and associated salts are attributed to 2003). The upper value of 2 ppm is close to the saturation limit
boiling; whereas lesser concentrations are due to conductive at the Rotokawa and Ngawha geothermal fields, which both
cooling and fluid mixing (Rae et al., 2011). The Na/K ratios have significant stibnite scaling due to pH change and cooling;
for most inclusions in this study range from 1.9 to 14.4 (avg at Ngawha ~3 t of stibnite precipitates every 6 months in heat
5.3) and overlaps with that for chloride waters in various geo- exchangers (Wilson et al., 2007). These concentrations for Sb
thermal fields irrespective of their overall total salt content; and also for As are in general two to three orders of magnitude
e.g., Palinpinon, 3.7 to 13.3 (avg 5.6; Rae et al., 2011), Ohaaki less than those determined by LA-ICP-MS for the FIAs mea-
4.2 to 12.3 (avg 6.0; Hedenquist, 1990) and Ogiri 2.3 to 11.7 sured in this study, which contain 0.3 to 988 ppm Sb and 3.33
(avg 7.1; Goko, 2000) and reflects the control by tempera- to 486 ppm As. Antimony is commonly incorporated into the
ture-dependent mineral-fluid equilibria. Several FIAs have host quartz and amethyst and therefore its absolute concentra-
Na and Ca, with K less than the detection limit or have Ca tion in many inclusions is poorly constrained. The LA-ICP-MS
concentrations greater than K. In the geothermal fluids, Ca transient signal profiles usually show a parallel rise of Sb and
mobility is controlled by retrograde solubility of calcite with Si, which suggests that Sb is also incorporated into quartz and
temperature, and generally Ca concentrations are <50 ppm, amethyst (Fig. 7B-C) likely in the form of micro- or nanoscale
but Ca mobility increases with both acidity and salinity (Ellis, inclusions. For that reason, we discuss only Sb values obtained
1959). Accordingly, in most deep reservoir fluids Na > K > in fluid inclusions hosted by Sb-free quartz (App. 1).
 Table 2. Composition of Reservoir Chloride Waters for Various Geothermal Fields from Around the World
780
  
Elements in geothermal waters
Temp Enthalpy pH Li Na K Rb Cs Ca Mg Cl– SO42– HCO3– B SiO2
Geothermal field/well (°C) (kJ/kg) (20°C) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

Broadlands Ohaaki, NZ1

BR25 (deep chloride) 290 1,269 8.1 1.9 895 189 1.8 1.6 1.4 0.04 1,429 14.5 300 51.6 1,050
BR6 (CO2-rich) 150 - 7.7 1.2 435 39 - - 2.6 - 28 15 2,284 1.2 180
Rotokawa, NZ2
RK4 310 1,450 5.75 7.4 446 136 1.0 1.0 1.6 0.01 806 5.43 172 n.m. 671
Wairakei, NZ3
41 ? - 8.5 12.4 1,175 172 2.4 2.2 24 0.005 2,113 23 - 5.8 540
Ngawha (Northland), NZ4
NG4 239 - 5.7 11.7 891 77 0.3 0.7 2.5 0.09 1,260 40 271 929 399
Ladolam, Papua New Guinea5
GW02 >250 1,100 7.36 n.m. 28,870 5,506 n.m. n.m. 30 - 21,710 32,704 2,984 n.m. 540
Palinpinon, Philippines6
PN14 (deep chloride) 272 1,341 6.85 14.7 3,160 858 4.4 2.8 59 0.06 6,009 10.6 - 69.1 909
OK7 (deep chloride boiling) 289 1,360 7.68 17.5 3,977 884 4.8 3.4 145 0.16 7,205 39.6 52 83.4 1,097
NJ2D (mixed chloride-sulfate) 281 1,248 3.62 9.3 2,304 408 2.5 1.8 36 12 4,098 954 - 51.3 1,003
Tongonan, Philippines7
Mahiao 401 (deep chloride) 300 1,700 6.6 n.m. 8,888 2,420 n.m. n.m. 302 n.m. 16,320 32 358 1,021
Mahiao 410 (deep chloride) ~320 1,740 6.6 n.m. 9,130 2,380 n.m. n.m. 237 n.m. 17,330 34 401 1,350
Mahioa 509 (margin) 249 1,090 7.7 n.m. 3,759 867 n.m. n.m. 171 n.m. 7,345 34 112 679
Mahanagdong MG1 (deep chloride) 267 1,210 8.1 n.m. 2,345 381 n.m. n.m. 21 n.m. 4,065 37 59 851
Mahanagdong MG2D (deep chloride) 261   982 8.1 n.m. 2,311 439 n.m. n.m. 28 n.m. 4,072 45 60 791
Otake-Hatchobaru, Japan8
Otake-9 ? - 8.6 4.8 1,050 132 n.m n.m 28.4 0.01 1,774 145 57 n.m. 531
SIMPSON ET AL.

Hatchobaru-4 ? - 7.0 10.9 2,250 277 n.m n.m 60.2 1.21 1,954 138 12 n.m. 679
Ogiri , Japan9
NT-A1 232 - 8.7 n.m. 441 53 11 n.m. 11 0.01 596 198 16 38.8 628
Fushime, Japan10
SKG-11 (sea water recharge + dilution) 330-340 1,153 7.23 n.m. 9,060 1,520 n.m. n.m. 1,290 1.4 18,400 (12,800) 31 - - 571
SKG-16 (sea water recharge) 250 1,717 3.8 n.m. 14,900 4,710 n.m. n.m. 1,540 17 31,800 (20,000) 36 - - 1,210
Olkaria, Kenya11
OW-305 1,179 - 1.4 453 87 n.m. n.m. 0.0 0.0 466 44 520 5.0 597
Coso, Unirws SA12
33-19 307 - - 36.3 2,801 700 n.m. n.m. 36.8 <0.10 5,121 11.6 30.2 113 700
77-7 249 - - 15.1 1,731 324 n.m. n.m. 25.3 <0.16 3,041 37.2 40.4 67 463
Salton Sea, United States13
SSSDP 2-14 (dissolution evaporites) 330 - - 209 54,800 17,700 132 142 28,500 49 158,000 53 - 271 580
Cerro Prieto, Mexico14
CP M-5 (meteoric + seawater) ~300 - - 12.6 5,004 1,203 5.3 0.9 284 0.33 9,370 3.6 - 10.5 569
El Tatio, Chile15
T3 253 - 7.7 31.1 3,510 168 n.m. 13.0 268 2.08 6,160 60 53 195 452
T7 250 - 7.0 45.2 4,840 830 n.m. 17.4 211 0.16 8,790 30 111 77 184

Notes: n.m. = not measured, - = no data 4 Sheppard and Giggenbach (1985) 8 Yanagase et al. (1983) 12 Moore et al. (1989)
1 Hedenquist (1990) 5 Simmons and Brown (2006) 9 Goko et al. (2000) 13 Lippmann et al. (1999),
2 Ellis and Mahon (1977) 6 Rae et al. (2011), 10 Okada et al. (2000) 14 Truesdell et al. (1981)
3 Krupp and Seward (1987) 7 Lovelock et al. (1982) 11 Omenda (1998) 15 Ellis and Mahon (1977)
 ADULARIA-SERICITE EPITHERMAL Au-Ag DEPOSITS, S. HAURAKI GOLDFIELD 781

A weak correlation between the Na content with either Sb

(4,397)
(6,035)
(ppm)

585   817

1,867
499   627
279   657

1,524
1,249
1,224
or As (Fig. 8) is not unexpected given that experimental stud-
Sb As Au Ag Hg Na Cl– ies have determined that both Sb and As are not complexed
with chloride in solution but are transported as the stable
neutral hydroxyl complexes of Sb(OH)3 and As(OH)3 over a
wide range of temperatures (Pokrovski et al., 2002; Zotov et
al., 2003). The stability diagrams for Sb(OH)3 and As(OH)3

(2,529)
(3,557)
(ppm)

940
presented in Figure 11 are constructed using thermodynamic
876
-
-
data published by Kelley (1960), Helgeson et al. (1978), Pok-
rovski et al. (2002), Zotov et al. (2003), and Perfetti et al.
(2008) applying the SUPCRT model and database (Johnson
et al., 1992). The mobility of both Sb and As depends on the
Table 3. Composition of Trace Elements in Chloride Waters for the Palinpinon and Several New Zealand Geothermal Fields

14.91 to 16.62
1.86 to 5.18

0.68 to 2.82

temperature, pH, and sulfur fugacity.

44 to 78

250  1.11
(ppb)

12.82

0.45 to 4.02   1.27 to 40.96   0.13

At ~225°C, stibnite is a stable Sb phase under acid con-
-
-

ditions, whereas valentinite is more stable in neutral and

(geothermal fields from New Zealand occur in the Taupo volcanic zone except for Ngawha in Northland)

alkaline environments. At a low sulfur fugacity along the

Elements in geothermal waters

pyrite-pyrrhotite buffer, stibnite occurs at a pH of less than

2.3; at a higher sulfur fugacity along the pyrite-chalcopyrite-
1,100 to 2,400
14.3 to 31.5

<0.1   6.0 to 14.1

10.1 to 19.1

5.05 to 7.22

bornite buffer, stibnite occurs at a pH that is less than 3.7 (Fig.

0.4 to 7.0
2.7 to 8
(ppb)

11). Our measured concentrations of Sb (0.3−988 ppm) are

less than the saturation limits over a wide range of pH values

from neutral to alkaline conditions.
At ~225°C, measured concentrations of As (3.33−486 ppm)
are less than the saturation limits at pH greater than 1.5,
2.12 to 2.67

assuming a low sulfur fugacity, and greater than pH 2.5 at a

0.3 to 1.5
0.7 to 2.1

0.5 to 1.0
0.5 to 0.7
7.8 to 23
(ppb)

3.90  0.6

higher sulfur fugacity (Fig. 11).

Limited LA-ICP-MS analyses of samples studied here show
that different FIAs within a single sample have trapped flu-
ids with variable element compositions and concentrations.
For example, four separate pseudosecondary FIAs in a quartz
3.12 to 4.86
1.20 to 1.40

2.90 to 3.20
0.17 to 0.43
0.38 to 0.77

crystal from the Martha deposit (AU 58166) show distinctly

(ppm)

n.m.
n.m.
1.54

different chemical compositions (App. 1). Most FIAs contain

Na, K, and Sb, except for FIA_4, where Sb concentrations
were less than the detection limits. Calcium was only detected
in FIA_2. Concentrations of Sb and As are greater in FIA_1
(Sb 67−204 ppm and As 31−36 ppm) compared to FIA_3 (Sb
0.48 to 0.54
0.18 to 0.23

0.04 to 0.58
0.47 to 1.69
0.47 to 2.08

1.72 to 1.85
0.23 to 0.37

1.2−18 ppm and As 6.4−18 ppm). Both FIA_2 and FIA_4

(ppm)

B-43   290   0.36

1.2

have comparable apparent salinities, but analyses of the latter

detected only Na and K, whereas the former contains measur-
able Na, K, Ca, Rb, Sr, Br, As, and Sb. These differences in
elemental compositions and concentrations suggest trapping
of fluids with differing chemistries. These differences could
be due to the modification of a single parent fluid by a combi-
Temp (°C)

260 to 295

M-6  322

>225
>235
R-5   320

W-239   255

N1 (outflow)   206
PN14   261

nation of chemical and physical processes, including mineral

dissolution and precipitation, water/rock interactions, boiling
and vapor loss, conductive cooling, and mixing.
Summary
Notes: n.m. = not measured, - = no data

The chemistry of individual fluid inclusions hosted in quartz

NG-13
NG-4
K-27
Well

veins from the Karangahake, Martha, Favona, and Waitekauri

epithermal deposits in New Zealand was determined by micro-
1 Simmons and Brown (2007)
2 Brown and Simmons (2003)

thermometry, LA-ICP-MS, and Raman spectroscopy. The ore

mineralization occurs in quartz veins within hydrothermally
altered andesite and dacite of the Coromandel Group. Quartz
Geothermal field/well

Broadlands-Ohaaki1

veins comprise colloform to crustiform bands that alternate

3 Rae et al. (2011)

with coarse-grained quartz and amethyst. The Au mineraliza-

tion occurs only in colloform to crustiform bands. Adiabatic
New Zealand

Palinpinon3
Kawerau1,2
Rotokawa1

Philippines

boiling is widely accepted as an effective mechanism for both

Wairakei1
Ngawha2
Mokai1

gold and SiO2 deposition, and fluid inclusion assemblages with

coexisting liquid- and vapor-rich inclusions were observed.

782 SIMPSON ET AL.

6 T=150°C 7 T=150°C

Py+Bo/Cpy
Po/Py

Realgar
5 6
Claudetite
4 Valentinite 5

Stibnite
988 ppm 4

As / log ppm
3
Sb / log ppm

/Py
3 486 ppm

Po
2
2
1 Sb(OH)3

y
1 3.3 ppm

p
o/C
0 0.3 ppm 0

+B
As(OH)3

Py
-1 -1
-2 -2
-3 -3
1 3 5 7 9 1 3 5 7 9
pH pH

6 T=225°C 7
Py+Bo/Cpy

Realgar
T=225°C
Po/Py

5 6
Valentinite 5
Stibnite

4
As / log ppm
4 As(OH)3

/Py
Sb / log ppm

y
3 988 ppm

/Cp
486 ppm

Po
3

Bo
2

Py+
2
1 Sb(OH)3
1 3.3 ppm
0 0.3 ppm 0
-1 -1
-2 -2
-3 -3
1 3 5 7 9 1 3 5 7 9
pH pH

T=300°C
Py+Bo/Cpy
Po/Py

6 7 Claudetite
T=300°C
/Py Realgar

5 6
Stibnite

5
/Cp

4 Valentinite
Bo

988 ppm 4 As(OH)3

Sb / log ppm

As / log ppm

3
Py+
Po

3 486 ppm
2
2
1 Sb(OH)3
1 3.3 ppm
0
0.3 ppm 0
-1 -1
-2 -2
-3 -3
1 3 5 7 9 1 3 5 7 9
pH pH
A B
Fig. 11. The stability diagrams for (A) Sb species and (B) As species as a function of pH, temperature, and sulfur activity.
The ranges of Sb and As concentrations measured by LA-ICP-MS in individual fluid inclusions are presented as well.

The presence of single-phase vapor-only fluid inclusions sug- are most comparable with chloride waters from the Palinpi-
gests that local flashing contributed to deposition of Au and non (~1,400−4,000 ppm), El Tatio (~1,900−5,000 ppm), and
Ag as well. Tongonan (~2,300−9,130 ppm) geothermal fields; although at
The concentration of salts in fluid inclusions from the the latter, reservoir chloride water comprises meteoric water
Hauraki goldfield (~260−13,700 ppm Na) generally exceeds and up to a 40% magmatic component. Hauraki goldfield
those for deep reservoir chloride waters in most geothermal inclusions and neutral chloride geothermal waters have simi-
fields of the nearby Taupo volcanic zone, New Zealand, which lar Na/K ratios, which reflect temperature-dependent min-
typically have less than 1,500 ppm Na. Sodium concentrations eral-fluid equilibria and allow estimation of the deep reservoir
 ADULARIA-SERICITE EPITHERMAL Au-Ag DEPOSITS, S. HAURAKI GOLDFIELD 783
fluid temperature by applying the Na/K geothermometer
(e.g., Verma and Santoyo, 1997).
Assuming boiling under hydrostatic conditions, samples
from the Karangahake deposit (Maria vein) were deposited
from low-salinity fluids (<3.9 wt % NaCl equiv) at tempera-
tures between 225° and 262°C and at depths of 270 to 575 m
below the former water table. The average calculated deep
reservoir fluid temperature is 287°C, and the steam loss
ranges between 8 and 17%.
The fluid inclusions in quartz from the Martha deposits
trapped dilute fluids with salinity less than 1.7 wt % NaCl
equiv. The coexisting liquid-rich (Th = 189°−225°C) and
vapor-rich inclusions (Th = 205°−243°C) suggest the forma-
tion at depths of 200 to 400 m below the water table. Accord-
ing to the Na/K geothermometer (Verma and Santoyo, 1997),
the deep reservoir fluid temperature was near 295°C and the
steam loss ranged between 15 and 23%. Pseudosecondary
inclusions in amethyst display salinity around 4.0 wt % NaCl
equiv and homogenization temperatures between 218° and
241°C. Secondary inclusions are slightly diluted (3.2−4.2 wt %
NaCl equiv) with homogenization temperatures between
213° and 242°C.
Fluid inclusions in quartz from the Waitekauri deposit have
Th values that range from 210° to 265°C and contain less than
1.2 wt % NaCl equiv. A thin quartz vein that occurs between
the Jubilee and Scotia deposits contains coexisting liquid- and
vapor-rich fluid inclusions; this reflects boiling conditions, and
the calculated formation depth under hydrostatic conditions
was 300 m below the former water table. The calculated deep
reservoir fluid temperature is around 283°C, and the steam
loss is estimated to be between 13 and 18%.
Individual analyses of fluid inclusions by LA-ICP-MS shows
that Na is the principal cation. Potassium, Ca, Rb, Sr, Sb, and
As were detected in all generations of fluid inclusions. Both
Au and Ag are less than their detection limits (ppm), but this
does not preclude their presence at the ppb level. The poor
correlation between the Na and either Sb or As suggests that
Sb and As are transported as neutral hydroxyl complexes of
Sb(OH)3 and As(OH)3.
Increased concentrations of Sb (up to 988 ppm) and As
(up to 486 ppm) together with the presence of adularia in
the studied quartz veins suggest their formation from neu-
tral to alkaline fluids. Moreover, neutral to alkaline pH con-
tributes to the mobility of Au and silica from their sources to
the deposition sites. The deposition is most likely related to
cooling of the liquid phase, increase in concentration of non-
volatile components (H4SiO4) in the remaining liquid phase,
and decrease in volatile content (H2S) during the adiabatic
boiling.
Limited LA-ICP-MS analyses show that different FIAs
within a single sample trapped fluids with variable element
constitutions and concentrations. These differences could be
a consequence of the modification of a single parent fluid by
mineral dissolution and precipitation, water/rock interactions,
boiling and vapor loss, conductive cooling, and mixing.
Future work on ore minerals is required to test whether the
primary fluid inclusions hosted by ore minerals such as sphal-
erite are similar to quartz-hosted inclusions and geothermal
fluids, or whether metal-enriched fluids are required to form
epithermal deposits.
Acknowledgments
We thank New Talisman Gold Mines Limited and Mur-
ray Stevens, Anton Barbar, and Peter Atkinson for access to
the Karangahake deposit and Newmont Waihi Operations for
access to the Martha, Favona, and Waitekauri deposits. In
particular, we would like to thank Luca Fedele for exceptional
help with running and data collection using the LA-ICP-
MS at the Fluids Research Laboratory, Virginia Polytechnic
Institute and State University, as well as data processing, and
Charles Farley for assistance with Raman spectroscopy. Edi-
torial comments from Shaun Barker, and constructive reviews
by Thomas Ulrich, Markus Waelle, Erin Marsh, and Janet L.
Slate helped to improve the manuscript and are greatly appre-
ciated. This research has been funded by the New Zealand
Ministry of Business, Innovation, and Employment, Newmont
Waihi Operations, and New Talisman Gold Mines Limited.
Any use of trade, product, or firm names is for descriptive
purposes only and does not imply endorsement by the U.S.
government.
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