New Zealand Journal of Geology and Geophysics

ISSN: 0028-8306 (Print) 1175-8791 (Online) Journal homepage: https://tandfonline.com/loi/tnzg20

The lithogeochemical signatures of hydrothermal

alteration in the Waihi epithermal district, New
Zealand

Shaun L.L. Barker, Shawn Hood, Rosie M. Hughes & Shannon Richards

To cite this article: Shaun L.L. Barker, Shawn Hood, Rosie M. Hughes & Shannon
Richards (2019): The lithogeochemical signatures of hydrothermal alteration in the Waihi
epithermal district, New Zealand, New Zealand Journal of Geology and Geophysics, DOI:
10.1080/00288306.2019.1651345

To link to this article: https://doi.org/10.1080/00288306.2019.1651345

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Published online: 26 Aug 2019.

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NEW ZEALAND JOURNAL OF GEOLOGY AND GEOPHYSICS
https://doi.org/10.1080/00288306.2019.1651345

RESEARCH ARTICLE

The lithogeochemical signatures of hydrothermal alteration in the Waihi

epithermal district, New Zealand
a,b b
Shaun L.L. Barker , Shawn Hood , Rosie M. Hughesa and Shannon Richardsc
a
School of Science, University of Waikato, Hamilton, New Zealand; bTransforming the Mining Value Chain, An ARC Industrial Transformation
Research Hub, CODES, University of Tasmania, Hobart, Australia; cOceanaGold Limited, Waihi, New Zealand

ABSTRACT ARTICLE HISTORY

Whole rock lithogeochemical data from the andesite rocks which host low-sulfidation Received 11 September 2018
epithermal gold veins in the Waihi district, New Zealand have been used to interpret Accepted 31 July 2019
hydrothermal alteration processes that variably altered the andesite rocks. The andesite host
KEYWORDS
rocks are interpreted to have similar primary chemical compositions throughout the Waihi Exploration geochemistry;
area, as reflected in similar ratios of immobile elements (eg Zr, Ti and other high field lithogeochemistry;
strength elements). The geochemical data reveal that elevated K/Al ratios occur in rocks epithermal; alteration;
proximal to low-Au–Ag deposits, reflecting adularia alteration in the host rocks associated mineralogy; pathfinder
with the upflowing hydrothermal fluids. Silicification of host rocks is achieved both by the elements; Waihi; New
addition of SiO2, as well as the destruction of plagioclase (reflected in the loss of CaO and Zealand
Na2O). The rocks have been variably altered, with calcite and pyrite abundance reflecting the
addition of carbon and sulphur. Pathfinder element (eg As, Sb) concentrations are variable
across the district, with high pathfinder element concentrations interpreted to reflect
proximity to hydrothermal fluid flow. Together, the results provide a district-scale overview of
hydrothermal alteration at Waihi, and emphasise the utility of lithogeochemistry for
classifying and quantifying hydrothermal alteration that can then be used to interpret
hydrothermal processes and assist mineral exploration.

Introduction
The Hauraki Goldfield in the North Island of New
Zealand (Figure 1) contains more than 50 low and
intermediate-sulfidation epithermal veins (Christie
et al. 2007). Epithermal veins continue to be of signifi-
cant interest for mineral explorers both in New Zeal-
and and globally. In this contribution, we review the
alteration typically associated with low-sulfidation
epithermal systems, and present new lithogeochemical
data to interpret hydrothermal alteration which sur-
rounds epithermal veins in the Waihi district in New
Zealand. This study focusses on how geochemical
data be used to interpret alteration mineralogy and
identify pathfinders to gold mineralisation in an
exploration context. For additional information on
alteration mineralogy and paragenesis in the Waihi
area, and nearby Golden Cross and Karangahake
deposits, readers are referred to Mauk and Simpson
(2007), Simpson and Mauk (2007, 2011), Simpson
et al. (2019) and Simpson and Christie (2019).
Low and intermediate-sulfidation epithermal gold
deposits in New Zealand are primarily found in the
Coromandel Volcanic Zone (CVZ) but are also found
at Ohakuri in the Taupo Volcanic Zone. Ohakuri is a
∼100,000-year-old deposit containing more than
2 MOz of gold at an average grade of < 1 gram per
ton (Grieve et al. 2006). Waihi hosts multiple Au–Ag
epithermal deposits including the large (> 7 Moz Au)
Martha deposit (Christie et al. 2007; Figure 1). The
Waihi area is an ideal study site for assessing the
mineralogical and geochemical alteration footprints
of epithermal vein systems, and associated Au–Ag
deposits, as the lithological host for mineralisation is
an andesite that is essentially chemically homogeneous
on the scale of sampling.
Low-sulfidation epithermal Au–Ag deposits are
typically found in magmatic arcs undergoing exten-
sion, and are associated with near-neutral pH fluids
at depth, which usually form a gangue mineral assem-
blage of quartz-adularia ± illite ± calcite (Simmons
et al. 2005). Near surface, fluids cool and can evolve
CO2, H2S and SO2 gases, which dissolve into water,
generating acidic fluids in shallow parts of the hydro-
thermal systems. Gold is precipitated through predo-
minantly boiling processes, although fluid mixing
may be a cause of metal precipitation (Weisberg
1969). Boiling promotes the separation of H2, H2S
and CO2 as gas species which lowers metal solubility,
promoting the deposition of precious and base metals,
and is a highly efficient process for metal precipitation.
Mixing may cause changes in oxidation state and pH,
as well as cooling and dilution of fluids, which can

CONTACT Shaun L.L. Barker shaun.barker@utas.edu.au

Supplemental data for this article can be accessed at https://doi.org/10.1080/00288306.2019.1651345
© 2019 The Royal Society of New Zealand
2 S. L. L. BARKER ET AL.

Figure 1. Maps of the Hauraki goldfield showing A, the geology and fault pattern (Skinner 1986, Brathwaite 1989; Edbrooke 2001;
Christie et al. 2007) and B, alteration zones and epithermal centres (veins). The inset maps indicates the location of the Hauraki
goldfield and the Taupo Volcanic Zone in the North Island of New Zealand. From Simpson et al. 2019 (this issue).

also drive metal precipitation (Simmons et al. 2005).
Thus, targeting veins prospective for mineralisation is
assisted by recognising the mineralogical and associ-
ated geochemical changes that are predicted to occur
during boiling and/or mixing, and in areas of hydro-
thermal outflow above boiling zones.
Characterising the mineralogical changes and min-
eral textures associated with hydrothermal fluid flow
related to epithermal gold mineralisation can be
detected using a variety of approaches. These include
logging of drill core for alteration features such as
abundance of veins, sulphide minerals or changes in
hardness (ie silicification), recognition of textures
associated with boiling (such as bladed calcite or
quartz), and staining for adularia (a variety of potass-
ium feldspar which is associated with upflowing and
boiling hydrothermal fluids) by cobaltinitrite. In the
last ten years, high sensitivity, relatively inexpensive
inductively coupled plasma-mass spectroscopy (ICP-
MS) data collected from whole-rock samples using a
near-total ‘4 acid’ digest (a mixture of HF, HCl,
HNO3 and HClO4 acids) has become widely available,
and is a powerful tool for interpreting mineralogical
changes, and identifying trace concentrations of
pathfinder elements, associated with mineralisation
(eg Halley et al. 2016). In addition, recent develop-
ments in portable x-ray fluorescence (pXRF) technol-
ogy mean that, with some care, accurate and precise

concentration data for some elements can be collected
in ‘real time’ during mineral exploration (eg Gazley
et al. 2014).
The principal concern with using lithogeochemical
data alone to assess alteration is that the chemical com-
position of the rock reflects the overall history of altera-
tion that has affected the sample, including original
lithological variation, pre-mineralising hydrothermal
events, the ore-forming hydrothermal system, and
any later overprinting events. While these influences
must always be considered and lithogeochemical data
interpreted with overprinting in mind, it is possible
that later hydrothermal alteration could cause signifi-
cant mineralogical changes without causing significant
metasomatism and consequent change in chemical
composition.
Review of alteration in low-sulfidation
epithermal systems
The general alteration footprint of low-sulfidation
epithermal quartz veins is well documented by numer-
ous case studies, and excellent summaries are provided
in Cooke and Simmons (2000) and Hedenquist et al.
(2000). Typically, epithermal quartz veins are found
within broad (regional) zones of propylytic alteration
consisting of chlorite, illite, illite-smectite and calcite,
which at shallow levels transitions to clay, carbonate
and zeolite minerals. Proximal to the quartz veins
(which are typically <20 m width, and usually a few
metres wide), there are alteration zones containing
quartz, adularia (which can occur both in veins and
surrounding wall rocks), and pyrite (Cooke and Sim-
mons 2000; Hedenquist et al. 2000; Simmons et al.
2005). Thus, there is a desire to identify and quantify
distal to proximal alteration features associated with
epithermal veins.
Much of our understanding of the patterns and con-
trols on alteration in epithermal systems is based on
alteration recognised within active geothermal systems
which have been explored for energy production. The
distribution of alteration minerals in active geothermal
fields is controlled by temperature and fluid compo-
sition (see summary of Browne 1978). In the deepest
parts of active geothermal fields accessed by geother-
mal wells, fluids are ∼ 300°C, generally reduced,
near-neutral pH, contain ∼ 0.1 to greater than 1 wt%
chloride, up to several weight percent carbon dioxide,
and up to hundreds of ppm H2S. These fluids are
broadly in equilibrium with a mineral assemblage rep-
resented by quartz ± albite ± adularia ± chlorite ± pyr-
ite ± calcite ± epidote. As the fluid rises, it begins to
boil, and quartz, adularia and calcite typically deposit
in high permeability pathways (eg fractures and
voids). In places, the neutral chloride waters can rise
to the surface directly and deposit silica sinter, or
may mix with surface groundwaters in an outflow
NEW ZEALAND JOURNAL OF GEOLOGY AND GEOPHYSICS 3
zone. As the fluid boils, the dissolved gases will separate
into the vapour and rise along discrete pathways. The
water vapour and gases may penetrate low permeability
rocks more easily than the fluid, and near surface can
dissolve into cool ground waters to form either CO2-
rich or acid-sulfate steam-heated waters. Carbon diox-
ide rich steam-heated waters contain high levels of dis-
solved carbon dioxide and are weakly acidic. They can
cause clay-mineral dominated alteration (eg smectite,
kaolinite, illite-smectite, illite), as well as form calcite
and siderite (Simmons and Browne 2000). Acid-sulfate
steam-heated waters form near surface, have lower pH
(pH∼ 2), and form alteration assemblages of opal, alu-
nite, kaolinite and pyrite (Simmons et al. 2005).
Geological setting
This case study focusses on alteration surrounding sev-
eral Au–Ag vein deposits in the Waihi area, including
the well-known Martha, Favona, and Correnso depos-
its (Braithwaite and Faure 2002; Simpson and Mauk
2007; Mauk et al. 2013). These deposits are all hosted
in the Waipupu Formation, an andesite-dominant for-
mation within the Late Miocene Waiwawa subgroup of
the Coromandel Group (Brathwaite and Christie
1996). The andesite consists of a plagioclase-phyric
two-pyroxene andesite with minor quartz phenocrysts
in the lower section (Braithwaite and Faure 2002;
Christie et al. 2007). Informally, within the mine,
these are often referred to as the quartz andesite and
feldspar andesite. Unaltered andesite contains pheno-
crysts of plagioclase, augite, hypersthene, minor quartz
and local hornblende, with accessory magnetite, apatite
and zircon. Rocks occur predominantly as flows, with
tuffs and thin carbonaceous lake beds in some parts
of the sequence which dip ∼40o to the east, suggesting
the sequence has been tilted towards the east (Sporli
and Cargill 2011). Thus, the western side of Waihi is
inferred to expose rocks from greater paleodepths
than rocks to the east. The andesites are unconform-
ably overlain by hornblende dacite to the east (Uretara
Formation), and then covered by various ignimbrites of
late Pliocene to early Quaternary age (Brathwaite and
Christie 1996). The samples analysed are mainly
from the lower part of the andesite sequence (Figure 2).
Methods
The data assessed during this study were obtained from
rocks collected during a systematic lithogeochemical
campaign by Waihi Gold Mine. Samples were collected
over an area of ∼ 14 km2 (Figure 2), with 691 samples
collected from ∼1 m split core of altered host rock free
from large visible veins (ie representing hydrother-
mally altered host rock with components of veins less
than 1 cm thick; Figure 3) by Waihi Gold Mine staff.
Sample locations are given on the ‘Mount Eden Old
4 S. L. L. BARKER ET AL.

a
th Favona
ar
M re
pi Section
Em l
Line
ya on
Ro Uni

nth
Moonlight

ara
-Am
Trio

Drill Traces wit h i n S t u d y

Quartz Veinin g 8 5 0 m R L
Quartz Veinin g 9 5 0 m R L
Postmineral I gn i m b r i t e s a n d A l l u v i u m
Uretara Format i o n ( p o s t m i n e r a l )
Waipupu Ande s i t e 0.1 0.5 1 km

Figure 2. Map and cross section of the Waihi area showing the approximate position of veins at different relative levels (red and
orange lines, projected to surface) and the distribution of whole rock sample points (black dots) along individual drill hole traces
(projected to surface). Economically important veins are named, and referred to in the text. Note the location of drill hole UW292
(see Figure 11).

Cadastral’ (MEO) grid, which is a Waihi local grid used
for exploration within 3 km of the Waihi Mine. The
MEO grid is offset from New Zealand Transverse Mer-
cator (NZTM Grid) by 5215389.166 (shift m N) and
1456198.997 (shift m E). The relative levels given in
Figure 2 are used in the mine, and are calculated as
sea level+1000 m.
Samples were crushed and split at the SGS labora-
tories in Westport, New Zealand, prior to be being
shipped to either the ALS Minerals laboratory in
Brisbane, Australia or the Ultratrace laboratory in
Perth For samples sent to ALS, samples were analysed
by a combination of methods as part of the CCP-
PKG03 analytical package. Major element chemistry
was determined by XRF analysis of lithium borate
fused beads, trace and rare earth elements were carried
out by ICP-MS on lithium borate fused samples dis-
solved in a ‘four acid’ mixture of HF–HNO3–HCl–
HClO4 acid, volatile elements were measured by aqua
regia digestion on rock powders, and total carbon
 NEW ZEALAND JOURNAL OF GEOLOGY AND GEOPHYSICS 5

Figure 3. Photographs showing examples of individual trays of drill core from which lithogeochemical data were collected, along
with calculated mineral abundances for those intervals for the most abundant minerals within each sample. The red boxes show the
interval from which core was split for geochemical analysis (see supplementary data table).

and sulphur were measured by infrared combustion
(LECO) analysis. Data quality was assessed via analysis
of several reference materials, including OREAS120,
SARM-3 and SARM-45. Major element XRF results
for SARM-3 and SARM-45 were within 3% (relative)
of the accepted values. Trace and rare earth element
values on the OREAS120 reference materials were
within 10% of the accepted value for all elements,
except for Sn (average reported value of 1.4 ppm,
accepted value of 0.67 ppm), which is below the
reported detection limit of the method (1 ppm), and
Ta (reported value = 0.68 ppm, accepted value =
0.55 ppm). The samples were submitted and analysed
as two separate batches to ALS. In order to check for
potential systematic chemical variation between
batches indicating problems with the analytical data,
the two batches of ALS samples were assessed using
split probability plots in IoGAS®. All elements show
very similar distributions excepting Sc, which shows a
significant distribution difference between the two
sample batches. Therefore, Sc data were not considered
further during this study. For samples sent to Ultra-
trace, only the major element data (measured by x-
ray fluorescence on lithium borate fused samples),
and total carbon and sulphur data (measured by infra-
red combustion) were considered in this study as the
6 S. L. L. BARKER ET AL.
analytical differences between the methods used for
trace element determinations were significantly differ-
ent. The major element and total carbon and sulphur
data were used only for calculated mineralogy determi-
nations (see below), and not for any mass transfer cal-
culations or assessment of trace element
metasomatism. Assessment of split probability plots
in IoGAS® for the three sample batches show very simi-
lar distributions for all major elements, carbon and sul-
phur. Thus the combined batches of geochemical data
are considered fit for purpose for determining mineral
proportions in samples.
Data were visually assessed and plotted using
IoGAS® geochemical analysis software (Imdex Lim-
ited). Ratios subsequently reported in this contribution
are reported as molar ratios, unless stated otherwise.
Estimates of the proportion of minerals within samples
were made using the weighted least squares method
outlined in Berry et al. (2011) and Escolme et al.
(2019). In brief, this approach finds a modal mineral-
ogy that most closely matches the major element geo-
chemical data, including C, S and H2O (estimated
from the loss on ignition component not explained
by total C and S). The minerals chosen were based
upon the most abundant minerals present in weakly
to strongly altered lithologies based upon previous
studies (Simpson and Mauk 2007; Booden et al.
2012) and unpublished quantitative scanning electron
microscopy data collected from Waihi by Hughes
et al (in preparation). The minerals chosen were plagi-
oclase (composition An = 93), albite, quartz, potassium
feldspar (adularia), calcite, Mg-rich chlorite, illite,
augite, magnetite, apatite, pyrite and montmorillonite.
Using this approach, variations in the solid solution of
plagioclase will be reported as mixtures of anorthite-
rich plagioclase and albite. The validity of the assumed
mineral assemblage can be assessed using the residuals
(representing major element content which cannot be
accounted for from the minerals used). Only 21
samples have residuals large enough that a mixture of
minerals from the list above cannot explain the major
element chemistry of the rock samples.
Mass transfer calculation methodology
Geochemical data reported as compositions are closed
(Aitchison 1982; 1986). This poses a problem when
looking for statistical correlation in compositional
data because values are relative, rather than absolute.
The log-ratio transform (Aitchison 1982; 1986; Egoz-
cue et al. 2003) is a solution to the constraints of closed
data. This method converts the compositional data into
real-number space, allowing the application of stan-
dard statistical methods. The Centred Log-Ratio
(CLR) transform was performed on a subset of
elements: Ag, Al2O3, As, BaO, Bi, CaO, C, Cd, Ce,
Co, Cr, Cs, Cu, Dy, Er, Eu, Fe2O3, Ga, Gd, Ge, Hf,
Hg, Ho, In, K2O, La, Li, LOI, Lu, MgO, MnO, Mo,
Na2O, Nb, Nd, Ni, P2O5, Pb, Pr, Rb, Re, Sb, Sc, S, Se,
SiO2, Sm, Sn, Sr, Ta, Tb, Te, Th, TiO2, Tl, Tm, U, V,
W, Yb, Y, Zn, and Zr.
Principal Components Analysis (PCA) is an effec-
tive way to identify groups of altered samples in ore
deposits (Gazley et al. 2015). Benefits of PCA are that
the dimensions of data are reduced, and elements
that are correlated can be grouped according to mem-
bership with resulting principal components (PC).
Both aspects improve clustering algorithm perform-
ance. Ten principal components were produced using
CLR transformed data for cluster analysis.
Samples were clustered using k-means (Ripley
1996), a technique that involves partitioning n obser-
vations into k clusters such that each sample is associ-
ated to the cluster belonging to the nearest mean. The
k-means algorithm was initialised with parameters set
to 50 re-runs and 300 maximal iterations. The optimal
number of clusters was identified using the Silhouette
scoring method available in the K-Means++ algorithm
provided in Biolabs Orange (Demšar et al. 2013), a
freely available machine learning multiplatform soft-
ware toolkit. The number of clusters k, to score, was
set to between two and ten. This K-Means++ approach
identifies an optimal number of clusters by combining
metrics of cluster dispersion and distance, where the
distance between clusters is maximised and the dis-
persion of samples associated with one cluster is mini-
mised (Kaufman and Rousseeuw 2005), and results are
scored using silhouette scores. The silhouette value for
each point is a measure of how similar that point is to
points in its own cluster, varying from −1 to +1, when
compared to points in other clusters. If most points in a
cluster have a high silhouette values, then the clustering
solution can be considered appropriate (Kaufman and
Rousseeuw 2005).
Mass-balance calculations have been used for dec-
ades to investigate bulk changes in geochemistry
between altered and unaltered rock pairs from the
same lithology (eg Grant 1986; MacLean and Barrett
1993; van Dongen et al. 2010; Carrasco and Girty
2015; Uvarova et al. 2017). Classical mass balance cal-
culations rely on sample vs sample comparisons, in
which two samples (one altered and the other being
an unaltered equivalent) are assumed to represent
entire alteration domains. Unfortunately, this
approach leads to inaccurate mass change elements,
as the variability of rocks in an area is not accounted
for. Mass balance results in this study were calculated
as per Ague and van Harden (1996), as adapted by
Hood et al. (2019). This statistically-robust approach
produces averaged estimates of mass change for entire
geological domains, using samples from within the
domains to produce element concentration matrices.
Quantification of mass changes of an open-system
requires that one or more immobile reference species
 NEW ZEALAND JOURNAL OF GEOLOGY AND GEOPHYSICS 7

be identified (Gresens 1967; Pearce and Cann 1973;

Grant 1986). To select which elements are immobile,
we opted to use a mathematical constraint, as described
by Woronow and Love (1990) and Ague and van
Harden (1996). In this approach, elements behaving
as immobile during alteration produce similar ratio
values when element concentrations in representative
protolith samples are divided by element concen-
trations in altered samples. Elements conforming to
this relationship included Al2O3, Ce, Cr, Dy, Er, Eu,
Ga, Gd, Hf, Ho, La, Nb, Nd, Pr, Sm, Ta, Tb, Th,
TiO2, Tm, V, Y, Yb, and Zr.

Results and discussion

Evidence for chemical homogeneity of host
andesites
The andesites at Waihi all have very similar rare earth
element patterns. Samples show light rare earth enrich-
ment and a flat MREE to HREE distribution (Figure 4),
characteristic of many andesites in the Coromandel
Zone (Booden et al. 2012). The Ce and Eu anomalies
are very similar for all samples. Ratios of Zr/Ti are
similar for the andesitic rocks analysed (Figure 5),
Figure 5. Scatter plots of Zr vs TiO2 and Al2O3. Note that the
varying between 0.03 and 0.05, similar to values pre- bulk of samples follow an approximately linear trend, consist-
viously reported from the Waipupu Formation of ent with relative immobility of Zr, Ti and Al during hydrother-
0.02–0.035 (Booden et al. 2012). A graph of Zr vs mal alteration.
Al2O3 (Figure 5) has a generally linear trend, with
some outlying samples (<10) having either significantly
elevated or significantly depleted Al2O3. Therefore, we alteration and therefore we consider that the andesites
consider that Al is also relatively immobile at Waihi for are essentially chemically homogeneous at a scale that
most samples (cf Figure 6). Overall, the host rocks is fit for purpose for considering the metasomatic
appear to have a very similar composition for elements changes that accompanied hydrothermal alteration.
that would be relatively immobile during hydrothermal As discussed below, Waipupu andesite geochemical

Figure 4. Chondrite normalised rare earth element values for the rocks sampled in this study (normalised using values of McDo-
nough and Sun 1995). Shown in black are the mean ± one sigma values, with individual samples plotted in grey. Note that almost
all the samples have a very similar REE composition, with varying REE concentration a function of variable dilution/enrichment by
hydrothermal processes (eg SiO2 addition).
8 S. L. L. BARKER ET AL.

Figure 6. (a) Plots illustrating the mass transfer that has occurred for different alteration styles of (a) smectite, (b) illite and (c)
adularia (see Figure 7 and text for alteration definitions). Twenty-four elements (Al2O3, Ce, Cr, Dy, Er, Eu, Ga, Gd, Hf, Ho, La, Nb,
Nd, Pr, Sm, Ta, Tb, Th, TiO2, Tm, V, Y, Yb, and Zr) were selected to produce an immobile reference frame for mass balance calcu-
lations (GMBE). A GMBE above 1 indicates overall mass loss during alteration (cf Hood et al. 2019).
 NEW ZEALAND JOURNAL OF GEOLOGY AND GEOPHYSICS 9

values defined in the literature (Booden et al. 2012) are 2007; Simpson et al. 2019; Hughes et al., unpub-
not identical to those for the andesite that host the lished data):
Waihi epithermal veins.
Illite: (K,H3O)(Al,Mg,Fe)2(Si,Al)4O10[(OH)2,(H2O)]
Adularia: KAlSi3O8
Alteration classification and quantification Kaolinite: Al2Si2O5(OH)2
Classifying alteration assemblages can be achieved Chlorite (clinochlore): (Mg,Fe)5Al(Si3Al)O10(OH)8
via several mechanisms, including identifying min- Montmorillonite: (0.5Ca,Na)(Al,Mg,Fe)4(Si,
erals using x-ray diffraction, petrography or infrared Al)8O20(OH)4.nH2O
techniques. Mineral alteration assemblages can also Pyrite: FeS2
be inferred from whole-rock chemical data. At Calcite: CaCO3
Waihi, as discussed above, the Waipupu andesite Alunite KAl3(SO4)2(OH)6
appears to have very consistent chemical compo- Quartz/chalcedony/opal: SiO2
sition. Alteration minerals most common to epither-
mal systems, including Waihi and the nearby Warren et al. (2007) presented a whole-rock geo-
Karangahake deposit, include (Mauk and Simpson chemical approach to characterise epithermal

Figure 7. Na/Al (molar) vs K/Al molar element ratio scatter plot. Note that representative values for typical igneous rocks, along
with the composition of key alteration minerals are plotted (Ms, muscovite; Il, illite; Mont, montmorillonite; Kfs, potassium feldspar;
Kln, kaolinite). Also shown are ternary diagrams which were used to classify kaolinite alteration from smectite clays.
10 S. L. L. BARKER ET AL.
Figure 8. Map showing the distribution of alteration styles at Waihi as defined on the basis of the lithogeochemical alteration
classification (see Figure 7).
mineralisation-associated alteration, using molar
element ratios (MER). This approach is used to identify
altered rocks containing adularia, illite, smectite, kaoli-
nite, and calcite. Classified samples can then be under-
stood in an alteration framework (Figure 7), and
alteration zones can be mapped spatially (Figure 8).
Use of MER alteration classification overcomes pro-
blems associated with closure, for example, the inac-
curate appearance of element concentration increase
or decrease, related to alteration, which is actually
caused by the mobility of other elements in the system.
The transition from smectite (montmorillonite) to
illite-smectite to illite (reflecting an increase in temp-
erature) is accompanied by increase in K/Al ratio.
Thus, the molar ratio of K to Al in a rock containing
illite only can be no greater than 0.33; any rock at
Waihi with a molar K/Al ratio greater than 0.33 must
therefore contain a proportion of hydrothermal potass-
ium feldspar (adularia), as there is no potassium feld-
spar in the igneous protolith. Kaolinite and smectite
forming due to cation removal during acidic alteration
will have low ratios of K/Al and Na/Al.
To classify alteration at Waihi, a Na/Al vs K/Al plot
was used (Figure 7; Madeisky and Stanley 1993). Wai-
pupu Formation andesites analysed by Booden et al
contain Na/Al ratios of 0.17–0.35, and K/Al ratios of
0.04–0.15. In contrast, altered andesite at Waihi
shows a range in values from Na/Al = 0–0.375, with
K/Al ranging from 0 to 0.825. Hughes and Barker
(2017) demonstrated that samples at Waihi with a K/
Al molar ratio greater than 0.275 contained adularia,
using a combination of portable XRF to measure K/Al
ratios and x-ray diffraction to identify samples contain-
ing adularia. Rocks at Waihi that contain Na/Al values
of <0.25 are interpreted to have had primary plagioclase
broken down via hydrolysis (ie addition of H+) to form
clay minerals and thus a loss of Na to the hydrothermal
fluid. Therefore, samples with low K/Al and Na/Al
ratios are interpreted to have an alteration assemblage
dominated by kaolinite and/or smectite, with near com-
plete destruction of primary plagioclase and removal of
Na and K by hydrothermal fluids. Using the K/Al and
Na/Al ratios, rocks at Waihi have therefore been geo-
chemically classified into (1) adularia dominated,
where Na/Al ratios are < 0.1 and K/Al ratios are greater
than 0.275, (2) adularia present samples with K/Al >
0.275 and Na/Al > 0.025; illite dominated samples
with Na/Al < 0.1 and K/Al between 0.225 and 0.275;
illite-smectite samples with Na/Al <0.0.025 and K/Al
between 0.1 and 0.225 and smectite dominated samples
where Na/Al <0.0.025 and K/Al is < 0.1. Moderately
clay altered samples are defined as having K/Al ratios
of <0.275 and Na/Al between 0.025 and 0.25. Least
altered samples have K/Al < 0.275 and Na/Al > 0.25,
comparable to unaltered values for Waipupu andesite
(Booden et al. 2012), and typical values for andesites
globally (Cox et al. 1979; see Figure 7).
This simple classification scheme outlined above was
compared to the calculated mineralogy approach. The
results of the weighted least squares calculated mineral-
ogy approach suggest that the modelled mineralogy clo-
sely matches the chemical data, with low residuals (eg
left over elements that cannot fit the data), excepting
21 samples that have particularly low Na/Al ratios
 NEW ZEALAND JOURNAL OF GEOLOGY AND GEOPHYSICS 11

Figure 9. Ranked variable maps for Waihi produced in IoGAS showing the relative abundances of quartz, potassium feldspar (adu-
laria), calcite, illite, montmorillonite and pyrite calculated from the geochemical data (see text for discussion). Symbols with cool
colours and small sizes are least abundant, warm colours and large symbol sizes are most abundant.

(see supplementary data). These samples likely contain Mass transfer calculations
kaolinite (in addition to or instead of smectite), which
The results of the mass transfer calculations are com-
was not included in the minerals list because otherwise
pared to elemental concentrations, and demonstrate
the list of minerals would be greater than the number of
that the amount of mass added (or removed) from
chemical components used. The calculated mineralogy
the andesite is approximately linearly correlated for
approach reveals similar trends in the distribution of
most elements. This indicates that the host andesite
adularia, illite and smectite (here modelled as mon-
has a highly homogeneous starting chemical compo-
tmorillonite) as that evaluated from the alteration dia-
sition, and that the effects of closure are minimal for
grams (compare Figures 8 and 9), with the advantage
most element studied. However, the advantage of cal-
that the calculated mineralogy approach allows the pro-
culating mass transfer changes is that it allows for the
portion of minerals within each sample to be estimated.
quantification of dilution effects (eg the apparent
For example, the calculated mineralogy results indicate
decrease of element concentrations due to the addition
that quartz abundance has a positive correlation with
of SiO2) or potential mass loss via destructive hydro-
illite abundance, but no clear correlation with adularia
thermal alteration. One constraint on the calculated
or pyrite (Figure 10).
addition and depletion values for elements relates to
At shallow levels, illite-smectite and smectite altera-
the selection of an immobile element reference frame,
tion has been identified above and around the Favona
which in turn is related to the selection of representa-
vein using x-ray diffraction (XRD) techniques (Simp-
tive least-altered protolith rocks in a system. Initial
son and Mauk 2007). Alteration classification and
mass balance calculations using published andesite
mapping (see Figures 7, 8 and 9) at Favona suggest
composition (Booden et al. 2012) produced spurious
smectite alteration at shallow levels, transitioning to
results. Waipupu andesite values reported in Booden
illite-adularia alteration at depth (see downhole min-
et al. (2012), as compared to values for the Waipupu
eral abundance plot in Figure 11), consistent with the
andesite measured at Waihi in this study are not inter-
XRD-based alteration distribution at Favona described
changeable because elements considered to be gener-
by Simpson and Mauk (2007). This suggests that the
ally immobile show systematic fractionation.
alteration classification at the ∼1 m scale at Waihi
Therefore, to assess mass change at Waihi, we choose
determined by lithogeochemistry is valid for assessing
to define a set of least altered samples (n = 14), based
alteration mineralogy. More broadly across the Waihi
on K/Al and Na/Al ratios that mostly closely resemble
area, our study has identified adularia alteration adja-
ratios of typical andesitic rocks and the values for the
cent to the northeastern end of the Martha vein system,
Waipupu formation defined by Booden et al. (2012),
surrounding Favona, and in several other locations
and have low concentrations of elements considered
(Figures 8 and 9). Samples with significantly adularia
as hallmarks of hydrothermal alteration. The samples
concentrations are most abundant around the Martha,
chosen have K/Al ratios of 0.07–0.17, and Na/Al ratios
Favona and Correnso veins deposits.
12 S. L. L. BARKER ET AL.

Figure 10. Abundance of quartz against plagioclase, pyrite, adularia and illite as determined from the calculated mineralogy
approach produced in IoGAS. Shown on each graph is a density contour, highlighting where the bulk of the samples plot.

Figure 11. Downhole plot of the calculated abundance of
montmorillonite (black line), illite (orange line) and adularia
(red line) in drill hole UW292 adjacent to the Favona deposit.
of 0.26–0.35. These samples have As concentrations
of 0.1–9.4 ppm, S between 200 and 5400 ppm, and
C between 400 and 3900 ppm, indicating that they
have undergone minor propylitic alteration. The
samples have a SiO2 concentration range between
58 and 66 wt%, somewhat higher than the SiO2
range defined for the Waipupu formation by Booden
et al. Therefore, these samples represent a least
altered (not unaltered) set of samples, and the chemi-
cal changes that are then calculated are relative to that
least altered reference frame. Overall, the elements
most added during illite and adularia alteration deter-
mined from the mass transfer calculations include
As, Sb, S, Tl, Te, Bi, Rb, Li, Cs, K2O, W, Se, Ag, Hg,
Mo, Sn (see Figure 6), with varying proportions
NEW ZEALAND JOURNAL OF GEOLOGY AND GEOPHYSICS 13
and degrees of addition depending on the style of
alteration.
The least altered sample definition chosen includes
some samples with elevated carbon (presumably con-
tained within calcite) and higher SiO2 than typical
andesite. This results in some samples having apparent
carbon depletion, which given the low starting carbon
for primary magmatic andesite seems unlikely. Our
results and chosen approach highlights the challenge
of defining least altered domains to accurately calculate
mass change, and suggests that rather than focussing
on the absolute values calculated, that the trends
obtained (relative mass loss/gain) across a hydrother-
mal system are the most valuable for assessing pro-
cesses that are relevant, such as silica addition
associated with hydrothermal upflow zones, or potass-
ium addition associated with adularia formation.
Examples of mass change are shown in Figure 12.
We note that the regions with the highest SiO2 gain
are associated with samples classified as being adularia
dominated or adularia added (compare Figures 9 and
12). This is consistent with the observation that the
core upflow regions of geothermal and low-sulfidation
epithermal systems is associated with adularia and
quartz mineralisation (eg Simmons and Browne 2000).
Feldspar destruction appears to be accompanied by
a release of Sr, with samples that contain abundant cal-
cite containing lower Sr concentrations than samples
with abundant plagioclase (Figure 13). This can also
be seen when assessing Sr mass transfer, with Na
mass loss associated with Sr mass loss (Figure 6).
Therefore, it is possible that elevated Sr (perhaps in dis-
tal carbonate minerals) could be seen in the outflow
zones of the Waihi epithermal system, and may form
a far-field pathfinder signature of feldspar destruction.
Carbonate and pyrite alteration
A plot of Ca against total C reveals that many of the
rocks analysed are close to a molar Ca:C ratio of 1:1,
indicating that most or all the calcium in the rock
(originally predominantly in plagioclase) is now pre-
sent as calcite, and the rocks are thus fully carbonate
altered (Figure 14). Generally, rocks in the western
part of Waihi have more carbon added to them than
rocks in the eastern part of Waihi (see calcite abun-
dance map in Figure 9), indicating that carbonate
was primarily added at deeper levels in the paleohy-
drothermal system. In general, the highest calcite abun-
dances are associated with illite-smectite and
moderate-clay alteration and are lowest in adularia
dominated samples (Figures 8 and 9). This is consistent
with the observation made at Broadlands-Ohaaki, that
calcite is minor to absent in the main upflow zone
associated with adularia development and silicification
(Simmons and Browne 2000). An assessment of the
relationship between Si and Ca mass addition or
14 S. L. L. BARKER ET AL.
Figure 12. Maps showing the calculated mass change (in %) for SiO2, K2O, CaO and Na2O across Waihi relative to the least-altered
samples (see text for details).
removal demonstrates that, as Si is added to the rock
mass, Ca is removed. Thus, silicification (eg formation
of quartz) in the rock mass is achieved partly by the dis-
solution of feldspar, not just by the addition of quartz
(Figure 10).
A graph of Fe vs S (Figure 15) demonstrates that many
samples are close to or immediately below a molar Fe:S of
1:2. High carbon, low sulphur samples sit on the fringes
of the system outboard from Martha, whereas samples
high in sulphur relative to carbon sit towards the middle
of the system and are associated with adularia dominated
samples (Figure 9). Generally, the highest pyrite concen-
trations are found around Favona, Correnso and south of
the Martha vein system (Figure 9).
Pathfinder elements
Pathfinder elements are those that indicate proximity to
an ore body. More broadly, we can consider pathfinder
elements to be those elements which are added to
rocks by hydrothermal fluids. Therefore the pathfinder
element concentrations and will reflect the concentration
of those elements in the fluid, and the physical and
chemical structure of the hydrothermal system which
control the transport and precipitation of those elements
in solution. Thus, pathfinder elements may be used to
make predictions about where ore may occur.
Concentrations of pathfinder elements can be con-
trolled by the solubility of the elements in hydrother-
mal solutions (and processes that change solubility)
as well as the growth of alteration minerals which are
able to take up those elements. Arsenic, Sb and Tl are
most enriched in rocks classified as adularia dominant,
with smectite and illite-smectite altered rocks also hav-
ing significantly elevated As (and to a lesser extent Sb;
Figure 16). Mercury is most elevated in samples
classified as kaolinite, smectite and moderately clay
altered, reflecting the precipitation of mercury at rela-
tively low temperatures (Figure 16).
District scale interpretation
The broad patterns evaluated in this study highlight
areas of:
(1) smectite to illite-smectite alteration with abundant
pyrite;
(2) potassic and adularia with abundant pyrite altera-
tion in the Martha and Favona areas, as well as an
area SE of the Martha-Empire-Royal veins;
(3) carbonate alteration without smectite.
We interpret these different distributions to reflect
the distribution of (1) lower temperature fluids (2)
upwelling, higher temperature alkali chloride waters
and (3) bicarbonate waters (cf Simmons and Browne
2000). It is important to note that the whole rock litho-
geochemistry reflects an integrated signal of all altera-
tion that has affected the rocks and that overprinting by
carbonate alteration (eg Mauk and Simpson 2007) may
have occurred in some areas.
The veins at Favona, Correnso and the broader
Martha system are surrounded by regions of potassic
alteration. Regions dominated by adularia are most
 NEW ZEALAND JOURNAL OF GEOLOGY AND GEOPHYSICS 15

Figure 13. Sr concentration plotted against (a) the calculated abundance of plagioclase (An93 composition) and (b) the calculated
abundance of calcite. Note the lack of correlation between calcite and Sr abundance.

Figure 14. Graph of Ca (weight percent) vs C (weight percent) concentrations in rocks from Waihi. Note that a significant number of
samples have very low Ca concentrations, which reflect Ca removal via feldspar destruction. Many samples sit close to a molar Ca:C
ratio of 1:1, meaning that all Ca in the rock occurs as calcite. The colour codes used for alteration are the same as defined in Figure 7.
16 S. L. L. BARKER ET AL.

Figure 15. Graph of Fe (weight percent) vs S (weight percent). Note that samples containing adularia typically have relatively high S
contents reflecting increased abundance of pyrite, while samples classified as least altered or moderately clay altered contain rela-
tively lower proportions of pyrite (eg further from the 1:2 molar ratio of Fe:S). The colour codes used for alteration are the same as
defined in Figure 7.

Figure 16. Split probability plots for Hg, Tl, As and Sb showing the distribution of these elements within various alteration styles
(using the alteration classification shown in Figure 7).

proximal to Favona, Correnso, and immediately west
of the Martha Pit, as well as in the southeastern area
(which is not near any recognised mineralised veins).
Strongly adularia altered rocks indicate more vigorous
hydrothermal fluid flow and boiling, which are most
likely to host gold mineralisation.
Conclusions and recommendations for explorers
The results of this study demonstrate the utility of
near-total analytical digestion for inferring the
alteration mineralogy of samples using whole-rock
geochemistry. Analytical results from four acid dissol-
ution can be interpreted with more confidence than
those from aqua regia digest (which will not digest,
or will only partially digest, many silicate minerals),
and can be used to map pathfinder minerals. In
addition, four-acid digestion will more completely dis-
solve resistate minerals that host immobile elements,
which are particularly valuable for mass balance calcu-
lations. Adularia and clay minerals in particular pro-
vide well-established proxies for distance to

mineralisation-related epithermal features. Exploration
companies should consider routinely acquiring four-
acid ICP-MS data. If this is not possible, a combination
of portable x-ray fluorescence, bench top x-ray fluor-
escence analysers (which place samples under vacuum
and can measure sodium, enabling evaluation of plagi-
oclase destruction by measuring Na/Al ratios) and por-
table x-ray diffraction analysers (which can be coupled
to XRF analyses to provide robust quantitative miner-
alogy) could be utilised on site in order to rapidly and
consistently determine and quantify alteration miner-
alogy, without the health and safety issues associated
with hydrofluoric-acid sample staining for adularia.
In addition, arsenic, a useful pathfinder element, is
easily measured by portable x-ray fluorescence with
detection limits appropriate for mineral exploration.
Acknowledgements
The authors thank Tony Christie for encouraging this sub-
mission, and the staff at Waihi from Newmont and Oceana-
Gold who supported and enabled this research, and provided
the analytical data. The authors particularly thank Lorrance
Torckler from OceanaGold for providing support through-
out this study and permission to publish this paper and
the data contained within, and Michael Belperio and Jeff
Bigelow from Newmont Mining Corporation. Stuart Sim-
mons and Scott Halley provided stimulating discussion on
alteration in epithermal systems. Ron Berry is thanked for
providing weighted least squares mineral abundance esti-
mates. Bob Braithwaite and Jeff Mauk provided reviews
that helped improve this manuscript. The Ministry for
Business, Innovation and Employment of the New Zealand
Government provided financial support through the Gold
Exploration Models Programme.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported by Ministry for Business Inno-
vation and Employment: [grant number Mineral Explora-
tion Models C05X1405].
ORCID
Shaun L.L. Barker http://orcid.org/0000-0002-4383-8861
Shawn Hood http://orcid.org/0000-0002-5680-7597
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