©2020 Society of Economic Geologists, Inc.

Economic Geology, v. 115, no. 2, pp. 443–453

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ASSESSING HYDROTHERMAL ALTERATION INTENSITY IN VOLCANIC-HOSTED MASSIVE

SULFIDE SYSTEMS USING PORTABLE X-RAY FLUORESCENCE ANALYSIS OF DRILL CORE:
AN EXAMPLE FROM MYRA FALLS, CANADA

Brian A. McNulty,1,†,* Nathan Fox,2 and J. Bruce Gemmell1

1Centre for Ore Deposit and Earth Sciences (CODES), University of Tasmania, Private Bag 79, Sandy Bay, Tasmania 7005, Australia
2W.H. Bryan Mining and Geology Research Centre, Sustainable Minerals Institute, University of Queensland, 40 Isles Road,
Indooroopilly, Queensland 4068, Australia

Abstract
Current portable X-ray fluorescence (pXRF) technology can rapidly and inexpensively yield concentrations
of geologically significant elements, typically with instrument detection limits below several tens of parts per
million. Based on conventional XRF whole-rock geochemical data, both the Ishikawa alteration index and the
chlorite-carbonate-pyrite index increase with proximity to sulfide mineralization at Myra Falls. However, avail-
able pXRF technology is typically unable to detect all the elements required to calculate these alteration indi-
ces. As a result, there is a need to utilize the elements that are readily detectable using pXRF and apply these
to hydrothermal alteration assessment.
We propose that Rb/Sr ratios provide a robust proxy for the Ishikawa alteration index and demonstrate that
conventional whole-rock XRF analytical results for Rb and Sr can be reproduced using pXRF analysis from drill
core surfaces. At Myra Falls, the Rb/Sr ratios vary from <0.1 for least altered rocks, 0.1 to 0.5 for weakly altered
rocks, 0.5 to 1.0 for moderately altered rocks, 1.0 to 2.0 for strongly altered rocks, and >2.0 for intensely altered
rocks. Downhole profiles of alteration intensity generated from systematic pXRF analysis of drill core surfaces
can be used to inform drilling and targeting decisions. The application of the Rb/Sr ratio as a proxy for altera-
tion intensity extends beyond this case study and can be applied to other hydrothermal systems that produce
phyllosilicate minerals as alteration products of feldspar.

Introduction energy dispersive-silicon drift detectors (ED-SSD) provide im-

Lithogeochemistry has been widely utilized in volcanic-hosted
massive sulfide (VHMS) deposit research to identify favorable
host rocks to mineralization using chemostratigraphic correla-
tions and for mapping hydrothermal alteration footprints (e.g.,
MacLean and Barrett, 1993; Barrett and MacLean, 1999;
Large et al., 2001a; Piercey, 2010). Determining the intensity,
zonation, and extent of hydrothermal alteration associated
with VHMS deposits has significant implications for mineral
exploration (Franklin et al., 1981; Large, 1992). Favorable al-
teration indicators may include broad Na2O depletion halos
and elevated whole-rock geochemical alteration indices at the
deposit scale with local, texture-destructive alteration of vol-
canic and sedimentary units at scales ranging between meters
and several hundreds of meters. Lithogeochemical studies in
VHMS systems typically utilize laboratory-based whole-rock
analyses to analyze elements including Na2O, MgO, Al2O3,
SiO2, K2O, CaO, and Fe2O3.
Portable XRF analyzers are increasingly used for applications
in geology, mining, alloy/materials, and environmental sectors
for rapid, field-portable geochemical analysis. Portable XRF
analyzers are typically capable of detecting elements with me-
dium to high atomic numbers (Z numbers) greater than sulfur
(Z = 16; Fig. 1). Recent developments in high-performance
†Corresponding author: e-mail, Brian.McNulty@utas.edu.au
*Present address: Mineral Deposit Research Unit, The University of British
Columbia, 2020– 2207 Main Mall, Vancouver, British Columbia V6T 1Z4,
Canada.
ISSN 0361-0128; doi:10.5382/econgeo.4714; 11 p.
Digital appendices are available in the online Supplements section. 443
proved sensitivity to elements with lower Z numbers (e.g., Mg,
Al, Si, and P) in newer instruments (e.g., Young et al., 2016).
Numerous studies over the past decade have evaluated the
application of pXRF analysis for discriminating lithology and
alteration in VHMS deposits. Peter et al. (2009) used pXRF to
assist in chemostratigraphic characterization of host rocks to
VHMS mineralization in the Abitibi greenstone belt, Canada,
by discriminating between unaltered and altered black shale
units. Similarly, Piercey and Devine (2014) demonstrated the
use of pXRF in providing fit-for-purpose data for discriminat-
ing lithogeochemical variations related to lithology, alteration,
and mineralization in exploration projects. Other studies have
shown that in situ pXRF analyses of fine-grained, volcanic
rocks yield robust immobile element ratios, which can be
used to distinguish intensely altered basalt to rhyolite units in
VHMS deposits (Ross et al., 2014b, 2016; Bourke and Ross,
2015; Fresia et al., 2017; McNulty et al., 2018). In this contri-
bution, we review commonly used lithogeochemical alteration
indices in VHMS deposit studies and assess the effectiveness
of the Rb/Sr ratio as a proxy for the Ishikawa alteration index
(AI) at Myra Falls.
Background on Alteration Indices
A number of alteration indices have been generated to cor-
relate lithogeochemical signatures of rocks with their ob-
served alteration mineralogy and intensity (Ishikawa et al.,
1976; Large et al., 2001a, b; Warren et al., 2007; Genna and
Gaboury, 2019).
Submitted: July 11, 2019 / Accepted: November 22, 2019

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 FIG 1

444 SCIENTIFIC COMMUNICATIONS

1 2
H He
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
11 12 12 14 15 16 17 18
Na Mg Al Si P S Cl Ar
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Ac ** Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Og

58 59 60 61 62 63 64 65 66 67 68 69 70 71
* Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
90 91 92 93 94 95 96 97 98 99 100 101 102 103
** Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

H elements not analyzed with pXRF instruments or out of scope of field analysis

Mg elements may be analyzed with specific pXRF instruments

Al elements may be analyzed with pXRF instruments → results are dependent on sample matrix and concentraon

Rb elements can typically be analyzed with pXRF

La elements are detected but cannot be analyzed individually with current pXRF technology

selected elements that are typically used in alteraon studies

Fig. 1. Periodic table showing atomic number (Z numbers) with pXRF instrumentation capabilities (modified from Lemière,
2018). * = lanthanide series, ** = actinide series.

The AI (eq. 1) quantifies the intensity of sericite (fine- Whole-rock Rb/Sr ratios have been used to characterize de-
grained white mica) and chlorite alteration in volcanic rocks grees of magmatic fractionation and as an indicator for post-
(Ishikawa et al., 1976). Large et al. (2001b) generated an al- magmatic alteration (e.g., Nockolds and Allen, 1953; Taylor,
teration box plot using whole-rock, major element oxide data 1965; Armbrust et al., 1977). Rubidium and Sr have ionic ra-
to correlate lithogeochemical signatures to alteration mineral- dii, electronegativity, and ionization potential similar to that of
ogy of volcanic rock types. The diagram uses the AI on the K and Ca, respectively (App. Table A1; Taylor, 1965). As such,
x-axis and the chlorite-carbonate-pyrite index (CCPI; eq. 2) Rb and Sr may be incorporated into K- and Ca-bearing min-
on the y-axis (Large et al., 2001b). erals (e.g., feldspars, phyllosilicates, and carbonates). Plimer
and Elliott (1979) proposed that the Rb/Sr ratio was useful in
Ishikawa alteration index (AI) = mineral exploration to assess styles of hydrothermal alteration.
K O + MgO Hydrothermal replacement of plagioclase by white mica min-

2
(1) erals (e.g., muscovite) results in a net loss of CaO (and Na2O)
K2O + MgO + Na2O + CaO and a gain in K2O (App. eq. A1, A2). During progressive al-
teration, Sr concentrations are reduced (loss of Ca-bearing
chlorite-carbonate-pyrite index (CCPI) = minerals), and Rb concentrations increase (gain of K-bearing
minerals) such that the Rb/Sr ratio reflects the intensity of
MgO + FeO
(2) white mica alteration (i.e., higher Rb/Sr ratios equate to more
MgO + FeO + K2O + Na2O intense alteration).
Because Na and Mg have low atomic numbers (Z = 11 and Myra Falls Geology
12, respectively), they are often problematic to measure and
accurately quantify using available pXRF instruments (Fig. 1; The Myra Falls VHMS deposits are located within Strathcona
e.g., Young et al., 2016). Provincial Park, near Buttle Lake, Vancouver Island, British

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 SCIENTIFIC COMMUNICATIONS 445

Columbia, Canada (Fig. 2A). It is one of western Canada’s Myra Falls VHMS Deposits
most productive VHMS mines, with total ore production ex-
ceeding 30 Mt at average grades of 5.5% Zn, 1.6% Cu, 0.6% Polymetallic massive sulfide mineralization at Myra Falls oc-
Pb, 2.0 g/t Au, and 54 g/t Ag (App. Tables A2, A3; R. Sawyer, curs in two stratigraphic members of the Myra Formation:
pers. commun., 2017). (1) the Lynx-Myra-Price member and (2) the H-W member
Vancouver Island comprises mid-Paleozoic to Early Juras- (e.g., Juras, 1987; Robinson et al., 1996; Fig. 2). The Lynx-
sic rocks of the Wrangellia terrane, overlying the mid-Pa- Myra-Price member orebodies are located in the upper Myra
leozoic Sicker Group (Nelson and Colpron, 2007). A num- Formation and oriented subparallel to the NW-SE–trending
ber of VHMS deposits and prospects occur in Devonian and Myra anticline (Fig. 2; e.g., Walker, 1985). The H-W member
late Carboniferous felsic volcanic rocks of the Sicker Group, orebodies are located in the lower Myra Formation on the
which are exposed in structural uplift zones throughout Van- northern limb of the Myra anticline (Fig. 2; e.g., Barrett and
couver Island (e.g., Muller, 1980; Ruks, 2015; Fig. 2A). At Sherlock, 1996). Sulfide mineralization occurs at two strati-
Myra Falls, the Sicker Group is divided into the late Devonian graphic positions in the H-W member VHMS deposits: (1)
Price and Myra Formations, the Carboniferous Thelwood and contact zone and (2) upper zone. The stratigraphic and sulfide
Flower RidgeFIGFormations,
2 and the Permian Buttle Lake For- mineralization relationships for the H-W member VHMS de-
mation (Juras, 1987). Post-Permian to pre-Triassic regional posits are summarized below.
burial metamorphism of the Sicker Group at Myra Falls com- Mineralization in the contact zone position occurs at the
prised low-grade greenschist and pumpellyite-actinolite facies base of the H-W member within 30 m of the Price Forma-
(Brandon et al., 1986; Juras, 1987). tion contact (Fig. 2C). Lithological units immediately above

A. B. C.
0 1000 0 mE 2000 mE 4000 mE
Myra Fa Buttle Lake
km lls mine
ka

L-M-P P
lease b
as

oundary
Al

L M
Mbr

Myra Forma…on
Myra C
CANADA Marshall Zone

k
5000 mN
8º

USA
12

Vancouver
Island Ridge Zone North
RZW B, RZN, MZ
Ridge Zone H-W
West Mbr HW, B

Price Forma…on
0 50
km 150 m
Bale Orebody
Dragon
Area Lynx Orebody Extension
Zone
Bu le Lake 5
HW
upli
Orebody Price Orebody
Campbell River
Bedingfield
upli 1 3000 mN
Myra Orebody
6 50
º Mine N
Tofino Structure VHMS Orebodies
Strait of

Myra An…cline L-M-P Member True N

Texada 0 500 48°
Faults H-W Member
Island
Georgia

m
Port
Alberni
Cowichan D. Mt. Phillips
+2000

+4000
+0

Lake Upli
+4500
Nanoose
upli Mt. Myra 250 m
Lithology
Carboniferous to Permian 2
3 +4000
Bule Lake Group Saltspring
4 Island Price Orebody
Devonian
Ju

Lynx Orebody
an

Sicker Group Ridge Zone

de

North Myra Valley Myra Orebody

Fu

Structure +3500
c

Fault
aS
tra

Thrust Fault Ridge Zone

it

West Gap HW Orebody

VHMS Mineraliza
on
Victoria +3000
1-6
1-5
2º
13

(see capon) Marshall Zone Bale Orebody Extension Zone

Fig. 2. A) Location map of Paleozoic strata of the Sicker and Buttle Lake Groups on Vancouver Island (after Massey et al.,
2005; Ruks, 2015). VHMS deposits and occurrences: 1 = Myra Falls deposits, 2 = Lara deposit, 3 = Lenora deposit, 4 = Jane
deposit, 5 = Dragon occurrences, 6 = Bedingfield occurrences. Inset shows location of Vancouver Island in Canada. B) Map
of Myra Falls VHMS deposits projected to surface (after Juras, 1987; Jones et al., 2006a). C) Schematic stratigraphic column
showing the relative stratigraphic position of the Lynx-Myra-Price (L-M-P) and H-W member VHMS deposits at Myra Falls
(McNulty, 2019). Abbreviations: B = Battle, L = Lynx, M = Myra, MZ = Marshal zone, P = Price, RZN = Ridge zone north,
RZW = Ridge zone west. D) Three-dimensional view of the Myra Falls VHMS deposits, looking north. Wireframe block
models and underground development polygons and polyline data were provided by the geology department of Nyrstar Myra
Falls operation.

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 446 SCIENTIFIC COMMUNICATIONS

contact zone position mineralization include argillite (HW
orebody; Juras, 1987; Barrett and Sherlock, 1996; Jones et al.,
2006b), chert (Battle orebody; Robinson et al., 1996; Jones
et al., 2006b), and felsic volcaniclastic siltstones and sand-
stones (West Block area; McNulty, 2019). Up stratigraphy
the sequence transitions into normally graded, intercalated
argillite and felsic volcaniclastic siltstone and sandstone beds,
with coherent rhyolite flows at the top of the H-W member
(e.g., Sinclair, 2000). In the Marshall zone, Ridge zone north,
West Block area and Ridge zone west localities, the basal vol-
caniclastic unit, comprising a 5- to 90-m-thick sequence of
polylithic conglomerate and sandstone, marks the base of the
H-W member (Chong, 2004; McNulty, 2019).
Mineralization in the upper zone position is located 75 to
100 m above the Price Formation and Myra Formation con-
tact (Fig. 2C). Sulfide mineralization in the upper zone is as-
sociated with coarse-grained volcaniclastic rhyolite and chert
(Ridge zone west; Chong, 2004) and felsic volcaniclastic brec-
cia, sandstone, and siltstone at the base and margins of co-
herent rhyolite flows (Battle orebody, Ridge zone north, West
Block area, and Marshall zone; Walker, 1985; Robinson et al.,
1996; T.J. Barrett and W.H. MacLean, unpub. report, 2000;
Sinclair, 2000; McNulty, 2019).
Previous Alteration Studies at Myra Falls
Whole-rock geochemical studies have been carried out on the
HW orebody (Barrett and Sherlock, 1996), Battle orebody
(Robinson et al., 1996; Sinclair, 2000; Jones, 2001), Marshall
zone (T.J. Barrett and W.H. MacLean, unpub. report, 2000),
and the West Block area (McNulty, 2019) to assess lithogeo-
chemical signatures related to hydrothermal alteration at
Myra Falls (Table 1).
Lithogeochemical characteristics of the H-W member
Andesite of the hanging-wall andesite member (n = 28) has in-
termediate to mafic Ti/Zr ratios (avg Ti/Zr = 79.2; Table 1), and
samples plot in the least altered field of the alteration box plot
(Fig. 3A). Rhyolite from the H-W member (n = 183) has felsic
Ti/Zr ratios (avg Ti/Zr = 12.9; Table 1). Least altered rhyolite
samples have AI <50 and CCPI <40, indicating a low abun-
dance of white mica, chlorite, and pyrite alteration minerals.
Weakly to intensely altered rhyolite samples form trends from
the least altered rhyolite field to the white mica- and chlorite-
pyrite–dominant alteration end members (Fig. 3B). Andesite
of the Price Formation (n = 98) has intermediate to mafic Ti/Zr
ratios (avg Ti/Zr = 58.8; Table 1). Least altered andesites have
AI >50 with CCPI values largely between 55 and 80 (Fig. 3C),
which is consistent with low abundance of white mica, pyrite,
and chlorite. Weakly to intensely altered andesite samples form
arrays from the least altered andesite field to the chlorite-pyrite-
and white mica–dominant alteration end members (Fig. 3C).
Previous Myra Falls Rb/Sr results
Two common alteration facies in VHMS deposits are white
mica-dominant and chlorite-dominant alteration zones that
develop from the hydrothermal alteration of primary plagio-
clase and volcanic glass (App. eq. A1, A2; e.g., Ishikawa et al.,
1976; Large, 1977; Franklin et al., 1981; Gifkins and Allen,
2001). Figure 3 illustrates the distribution of Rb and Sr and
the relationship between the Rb/Sr ratio and the AI and CCPI

Table 1. Review of Conventional Whole-Rock Lithogeochemical Data

Chlorite-carbonate-
Ti/Zr Rb/Sr Ishikawa alteration index pyrite index

Facies Location n Avg Range Avg Range Avg Range Avg Range
HWA T1 3 64.5 52.3–73.3 0.01 0.01 33 26–42 76 68–81
HWA M2 20 75.1 22.0–155.0 0.36 0.01–2.47 45 26–66 70 48–91
HWA WBA3 1 98.1 0.00 28 89

QFP T1 3 11.2 10.4–11.7 0.34 0.12–0.50 53 31–79 50 50–52

QFP HW4 18 13.5 9.3–19.4 0.29 0.01–0.59 56 18–82 52 26–96
QFP B5 49 11.0 7.0–20.6 0.90 0.05–11.20 64 14–97 40 15–77
QFP M2 91 12.2 6.8–17.1 1.43 0.01–7.99 66 6–98 37 14–67
QFP WBA3 3 9.1 9.0–9.4 0.48 0.05–0.89 67 19–91 27 14–37

Fvc HW4 6 13.7 11.1–18.4 0.93 0.06–2.33 64 30–94 46 36–63

Fvc B5 22 20.9 8.0–76.9 1.36 0.01–3.55 77 27–99 48 9–71

A T1 3 37.2 29.1–52.1 0.03 0.01–0.07 31 26–38 59 51–68

A HW4 22 69.6 38.7–96.2 0.59 0.00–2.62 55 26–96 73 40–99
A B5 52 64.5 35.8–99.9 3.23 0.02–14.00 90 33–98 72 34–94
A M2 15 63.7 29.8–113.3 0.50 0.00–1.26 54 37–82 68 41–93
A WBA3 14 59.2 38.7–73.6 0.55 0.21–1.67 60 44–84 63 54–82

Facies abbreviations: A = Price Formation andesite, Fvc = felsic volcaniclastic rocks, HWA = hanging-wall andesite member, QFP = quartz-feldspar-phyric
coherent rhyolite
Location abbreviations: B = Battle orebody, HW = HW orebody, M = Marshall zone, T = Thelwood Valley, WBA = West Block area including the Ridge
zone north
Data sources: 1Sinclair (2000), 2Barrett and MacLean (2000), 3McNulty (2019), 4Barrett and Sherlock (1996), 5Robinson et al. (1996)

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 FIG 3
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A. B. C.
100 100 100
ep, ca dol ank n = 28 chl, py ep, ca dol ank n = 183 chl, py ep, ca dol ank n = 98 chl, py
90 90 coherent rhyolite 90
Strongly altered
felsic volcaniclasc rocks wm-chl-py
80 80 80
least altered
andesite field 70 least altered
70 70 andesite field

60 60 60
y
l- p
-ch

CCPI
wm

CCPI
CCPI

50 50 50
least altered weakly altered
rhyolite field
40 40 40 chl-wm-py
Rb/Sr wm
30 <0.1 30 30
0.1-0.5
0.5-1.0 strongly altered
20 wm 20 wm 20 chl-wm-py wm
1.0-2.0
>2.0
10 10 10
alb Ksp alb Ksp alb Ksp
0 0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
AI AI AI
D. E. F.
n = 28 n = 183 n = 98

1
2
1
2
1
2

0.5
0.5
0.5

140 140 140

120 120 120

100 inc 100 inc 100 inc

re re re
as as as

Rb (ppm)
Rb (ppm)
Rb (ppm)

in
in
in

.1 .1 .1
=0

ga
=0 =0
ga
ga

80 80 80
/Sr /Sr /Sr

lte
lte
lte

Rb Rb Rb

ra
ra
ra

o
o
o

n
n
n

60 60 60

40 40 40

20 20 20

0 0 0
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800
Sr (ppm) Sr (ppm) Sr (ppm)
G. H. I.
100 100 100
n = 28 n = 183 n = 98
90 90 90

80 80 80

70 70 70

60 60 60

50 50 50
AI
AI
AI

40 40 40

30 30 30

20 20 20

10 10 10

0 0 0
0.001 0.01 0.1 1 10 20 0.001 0.01 0.1 1 10 20 0.001 0.01 0.1 1 10 20
Rb/Sr Rb/Sr Rb/Sr
Fig. 3. Review of published whole-rock geochemical data for the hanging-wall andesite (A, D, G), coherent rhyolite and volca-
niclastic rhyolite rocks of H-W member (B, E, H), and Price Formation (C, F, I) stratigraphy. A-C) AI versus CCPI alteration
box plot of Large et al. (2001b). D-F) Sr versus Rb diagrams. G-I) Comparison of the Rb/Sr ratio versus AI. The smaller symbols
highlight samples with Rb <25 ppm (n = 26). See Table 1 for whole-rock geochemical data set sources. Abbreviations: alb =
albite, ank = ankerite, ca = calcite, chl = chlorite, dol = dolomite, ep = epidote, Ksp = K-feldspar, py = pyrite, wm = white mica.

indices in whole-rock geochemical analyses at Myra Falls. In G) and can largely be attributed to diagenetic alteration pro-
general, the observed increases in the Rb/Sr ratios correspond cesses (Sinclair, 2000). While there is considerable overlap in
to increases in the AI values (Fig. 3G-I). the Rb/Sr ratios from the H-W member data set, overall the
The low (or weak) alteration intensity in the hanging-wall Rb/Sr ratios increase with increasing AI values (Fig. 3E, H).
andesite member is reflected by the low Rb/Sr ratios (Fig. 3D, Samples with Rb contents <25 ppm are not considered to be

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 448 SCIENTIFIC COMMUNICATIONS
significantly altered, whereas least to weakly altered samples
have Rb/Sr ratios that are <0.5, and moderately to strongly
altered samples have Rb/Sr ratios >0.5 (Fig. 3E). Andesite of
the Price Formation is considered to be least altered where
the Rb/Sr ratio is <0.5, whereas weakly altered samples have
Rb/Sr ratios between 0.5 and 1.0 with strongly to intensely al-
tered samples having Rb/Sr ratios >1.0 (Fig. 3F, I). The above
review of Rb/Sr signatures is from conventional whole-rock
geochemical data, from which AI and CCPI values were cal-
culated. The following sections document the collection and
interpretation of new Rb/Sr data using pXRF analysis.
Methodology
Portable XRF analysis of drill core
Portable XRF measurements were collected from BQ drill
core offcuts ranging between 5 and 10 cm in length. Two
data sets are presented in this contribution. The first data set
consists of 65 samples, which have corresponding whole-rock
lithogeochemical data from Sinclair (2000) and McNulty et
al. (2018). The second data set consists of new pXRF analyses
carried out on 300 drill core samples from underground drill
holes without corresponding whole-rock data.
For each drill core sample, three pXRF analyses were col-
lected from the sawn flat surface, which was cleaned and
dried to be free from dust. To minimize the effect of geo-
logic heterogeneity, the groundmass was the focal target area
for analysis of coherent rock types, whereas in volcaniclastic
rocks, the matrix was preferentially targeted.
Portable XRF instrumentation and calibration
Portable XRF analyses were collected at the Centre for Ore
Deposit and Earth Sciences (CODES), University of Tas-
mania, Australia, using an Olympus Innov-X Delta Premi-
um pXRF analyzer, with a rhodium anode X-ray tube with
a maximum voltage of 40 kV and 4-W power, and a 20-mm2
ED-SDD window. Analyses were completed in SOIL mode,
which operates at 40 kV for beams 1 and 2 measuring U, Sr,
Zr, Th, Mo, Ag, Cd, Sn, Sb, Fe, Co, Ni, Cu, Zn, W, Hg, As,
Se, Pb, Bi, and Rb, and 15 kV for beam 3 measuring P, S,
Cl, K, Ca, Ti, V, Cr, and Mn. The Innov-X Delta Advanced
PC software utilizes a Compton normalization algorithm to
determine elemental abundances with detection limits in the
<10- to 50-ppm range (Jenkins, 1999; Innov-X Systems Inc.,
2010; Hall et al., 2013). The total measurement integration
time interval was 210 s, with approximately 55- to 60-s/beam
active runtime. The total three-spot pXRF measurement run-
time was about 11 min/sample.
Calibration factors were calculated from a least squares
linear model using the pXRF-measured value (x) to predict
the standard value (y) of the reference material (McNulty et
al., 2018). For this application, the limit of detections for Rb
and Sr were calculated using the method of Meier and Zünd
(1993) and are 1.2 and 4.3 ppm, respectively.
Sampling precision and measurement uncertainty
The raw pXRF concentration data were multiplied by their
respective calibration factor for each element prior to sample
averaging. The sampling precision is in effect an estimate of
the geologic heterogeneity of the sample (e.g., Markowicz,
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2008). The total measurement uncertainty (%Gtot) for cali-
brated pXRF results was determined by the square root of the
sum of the squares of the relative standard deviation (RSD)
and root mean squared (RSM) of the instrument, and the
RSD of the sample (Barford, 1985). The total measurement
uncertainty is expressed as absolute error bars on bivariate
plots and downhole profiles.
Results
Comparison of three-spot pXRF and conventional XRF results
A comparison of the corrected and averaged three-spot pXRF
data with the conventional XRF results illustrates that the two
methods produce similar results. Rubidium, Sr, and Rb/Sr are
well correlated, with Spearman rank coefficient (rs) values of
0.94, 0.99, and 0.98, respectively (Fig. 4A-C). Overall, the
conventional XRF Rb/Sr ratio increases as the AI value in-
creases. Importantly, the pXRF Rb/Sr results mirror the pro-
file of the conventional whole-rock Rb/Sr results (Fig. 4D).
Rb/Sr ratios from the West Block area and the Ridge zone
north
Bivariate Sr versus Rb diagrams (Fig. 5) were used to assess
hydrothermal alteration intensity for each logged rock type in
the West Block area (eight drill holes) and Ridge zone north
(one drill hole). Based on the comparison of the Rb/Sr ratios
and the AI values from conventional whole-rock XRF analysis
(Fig. 3) the following Rb/Sr alteration intensity classification
is proposed: (1) least altered rocks have Rb/Sr <0.1, (2) weakly
altered rocks have Rb/Sr between 0.1 and 0.5, (3) moderately
altered rocks have Rb/Sr between 0.5 and 1.0, (4) strongly al-
tered rocks have Rb/Sr between 1.0 and 2.0, and (5) intensely
altered rocks have Rb/Sr >2.0.
The coherent andesite flow and volcaniclastic rocks strati-
graphically above the H-W member in the West Block area
display least altered to weakly altered Rb/Sr signatures
(Fig. 5A). Coherent rhyolite of the H-W member in the
West Block area and Ridge zone north localities has weak
to strong Rb/Sr alteration signatures (Fig. 5B), whereas vol-
caniclastic and sedimentary rocks have moderate to intense
Rb/Sr alteration signatures (Fig. 5C-D). Andesites of the
Price Formation have least altered to intensely altered Rb/
Sr signatures (Fig. 5E).
Applications for Mapping Alteration Intensity
Downhole profiles of the averaged, three-spot pXRF data il-
lustrate the application of systematic pXRF analysis to map-
ping alteration intensity at Myra Falls (Fig. 6). Drill hole
RN18-0224 from the Ridge zone north orebody intersected
contact zone, polymetallic sulfide mineralization. The down-
hole Rb/Sr profile is similar to that observed at the Battle
orebody (Fig. 4D), showing an increase in the Rb/Sr ratio
downhole toward polymetallic sulfide mineralization. Sulfide
mineralization is coincident with Rb/Sr ratios >1.0. The high-
est Rb/Sr ratios (>3.0) occur in the intensely altered footwall
andesite of the Price Formation (Fig. 6).
Drill holes BG18-3907 and BG18-3902 from the West Block
area are located approximately 400 m west of RN18-0224. In
the West Block area, polymetallic sulfide mineralization is less
well developed compared to the Ridge zone north orebody.
 FIG 4
SCIENTIFIC COMMUNICATIONS 449

A. D.
rs = 0.94 1420 mE

1
1:
Lithology AI Rb/Sr Rb/Sr [pXRF]
100 0m

75
Rb (ppm)

50

25

LOQ 2.2
0
0 25 50 75 100
Rb  pXRF (ppm) 50 m
B.
rs = 0.99
1
1:

800

600
Sr (ppm)

400

200 100 m

LOQ 9.5
0
0 200 400 600 800
Sr  pXRF (ppm)
C. 0 50 100 0 1 2 3 0 1 2 3
rs = 0.98
1
1:

3 Correlaon Plots H-W member Geochemistry

hanging-wall andesite coherent rhyolite whole-rock data (Sinclair, 2000)
n=8
felsic pXRF data this study
felsic volcaniclasc rocks
n=10 volcaniclasc rocks
Rb/Sr (ppm)

2
Rb/Sr
coherent rhyolite chert
n=11 <0.1 → least altered
0.1-0.5 → weakly altered
chert Mineralizaon 0.5-1.0 → moderately altered
1
n=4
massive sulfide 1.0-2.0 → strongly altered
argillite
n=4 >2.0 → intensely altered
Price Formaon
Price Formaon
n=28 coherent andesite
0
0 1 2 3
Rb/Sr  pXRF (ppm)

Fig. 4. Series of correlation plots (A-C) and downhole geochemical profiles (D) demonstrating the fit between the conven-
tional whole-rock geochemistry and the three-spot pXRF analysis. Note the strong positive correlation between analytical
methods for Rb, Sr, and Rb/Sr (A-C). D) Composite graphic log of the Battle orebody from cross section 1420 mE (adapted
from Sinclair, 2000). Error bars are expressed as the total measurement uncertainty (%Gtot) for pXRF measurements, and
error bars smaller than the symbol are not plotted.

Sulfide mineralization typically occurs as fine-grained dis-
seminations and wispy stringer veins of sphalerite and chal-
copyrite in both contact zone and upper zone positions. The
absence of well-developed, semimassive to massive sulfide
zones is reflected by the low Cu and Zn assay results (Fig. 6).
While the Cu and Zn concentrations are lower, these zones
display Rb/Sr ratios typically >1.0. The Rb/Sr ratios mimic the
variability of the Zn and Cu assay results, with elevated Rb/Sr
coincident with elevated base metal content (Fig. 6).
Rb/Sr ratio compared to logged hydrothermal alteration facies
The downhole profiles of Rb/Sr appear to correlate with the
intensity and mineralogy of the logged alteration facies. The
logged alteration of the Price Formation includes chlorite-
sericite-pyrite and chlorite-calcite ± pyrite facies (e.g., Sinclair,
2000). In the case of the intensely altered footwall andesite that
occurs below the contact zone sulfide mineralization in the
Ridge zone north, chlorite-sericite-pyrite alteration is abun-

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 450 SCIENTIFIC COMMUNICATIONS

A. B. C.
2

2
1

0.5

1
0.5

0.5
140 140 140

120 120 120

100 0.1 100

=0
.1 100
=0
.1
r=
/S /Sr /Sr
Rb Rb Rb

Rb (ppm)
Rb (ppm)
Rb (ppm)

80 80 80

60 60 60

40 40 40

20 20 20

0 0 0
0 200 400 600 800 0 200 400 600 800 0 200 400 600 800
Sr (ppm) Sr (ppm) Sr (ppm)
D. E.
Symbols
2
2

1
1

0.5
0.5

140 140
andesic volcaniclasc rocks
n=51
120 120
coherent andesite
n=52
100 .1 100 .1 felsic volcaniclasc rocks
=0 =0 n=29
/Sr /Sr
Rb Rb
Rb (ppm)
Rb (ppm)

80 80 coherent rhyolite
n=37
chert
60 60 n=6
basal volcaniclasc unit
40 40 n=17
Price Formaon
n=94
20 20
Rb <25 ppm
n=14
0 0
0 200 400 600 800 0 200 400 600 800
Sr (ppm) Sr (ppm)

Fig. 5. Summary of Rb and Sr results from downhole three-spot pXRF analyses. A) Coherent andesite flow and andesitic
volcaniclastic rocks. B) Coherent rhyolite of the H-W member. C) Felsic volcaniclastic rocks and chert of the H-W member.
D) Basal volcaniclastic unit. E) Coherent and autobreccia andesite of the Price Formation. Error bars are the total measure-
ment uncertainty (%Gtot). Note that red symbols denote samples with Rb <25 ppm.

dant and coincident with Rb/Sr ratios >2.0 (Fig. 6; App. Fig.
A1A-B). The elevated Rb/Sr ratios correspond with texturally
destructive alteration characterized by replacement of plagio-
clase phenocrysts by sericite and chlorite. Chlorite-calcite ±
pyrite alteration is typical of footwall andesite below sporadic
sulfide mineralization in the West Block area. Here, the Rb/
Sr ratio ranges from <0.1 to 1.0 (Fig. 6). This alteration facies
is not texturally destructive, with plagioclase phenocrysts being
preserved and, overall, the rocks containing less chlorite (App.
Fig. A1C).
Hydrothermal alteration facies affecting the H-W member,
the host rocks to VHMS mineralization, include quartz-sericite
± pyrite, chlorite-sericite-pyrite, and quartz (chert). In the West
Block area, disseminated and stringer-style sulfide zones are as-
sociated with chlorite- and sericite-altered felsic volcaniclastic
rocks with Rb/Sr ratios between 0.5 and 1.0 (Fig. 6), whereas
semimassive sulfide zones are hosted in felsic volcaniclastic
rocks with Rb/Sr ratios >1.0 (App. Fig. A1D-E). Moderate to
strong chlorite-sericite-pyrite alteration of the basal volcanicla-
stic unit typically produces Rb/Sr ratios >0.5 (App. Fig. A1F-
G). Felsic volcaniclastic rocks in the Ridge zone north orebody
with quartz-sericite-pyrite alteration have Rb/Sr ratios >1.0 and
are typical of massive to semimassive sulfide zones in the Ridge
zone north orebody (Fig. 6; App. Fig. A1H-I).
Chlorite-calcite and chlorite-epidote-calcite alteration fa-
cies are present throughout the hanging-wall andesitic stra-
tigraphy (Fig. 6). With the exception of a few examples, these
rocks have Rb/Sr ratios of <0.1 and are only weakly altered
(App. Fig. A1J-L).
Discussion and Exploration Implications
This study has identified a proxy measurement for conven-
tional whole-rock geochemical alteration indices, which uti-
lizes widely available and field deployable pXRF technology.
The hydrothermal alteration mineral assemblages associated
with polymetallic sulfide mineralization in the H-W member
VHMS deposits are (1) quartz-sericite-pyrite, (2) sericite-
chlorite-pyrite, and (3) chlorite-calcite-pyrite. The AI has
previously been used to quantify the intensity of these hydro-
thermal alteration facies at Myra Falls (Fig. 3).
Current pXRF analyzers are unable to measure all the ele-
ments needed for the AI calculation. Sodium (Z = 11) cannot
be directly measured but has been estimated from other ele-
ments using machine learning approaches (Schnitzler et al.,

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 RN18-0224 Alt/ BG18-3907 Alt/ BG18-3902 Alt/
Lithology Min Rb/Sr Cu (%) Zn (%) Lithology Min Rb/Sr Cu (%) Zn (%) Lithology Min Rb/Sr Cu (%) Zn (%)
0m 0m 0m
J

by Columbia University user

K

50 m I 50 m 50 m

A L

100 m 100 m 100 m

0 1 2 3 4 5 2 1 0 10 20

py
hanging-wall andesite D
andesic volcaniclasc rocks E
(massive, fine- to medium-grained, breccia)
andesite flow Mineralizaon
massive to F G
coherent and hyaloclasc semimassive sulfide
H-W member Andesite - Price Formaon C
coherent and
coherent rhyolite 150 m
autobreccia 150 m
felsic volcaniclasc rocks
(medium- to coarse-grained) Structure and Intrusions

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argillite and chert fault zone
SCIENTIFIC COMMUNICATIONS

basal volcaniclasc unit mafic dyke

Logged alteraon and mineralizaon

disseminated semimassive
chl-ca qtz-ser qtz sulfide sulfide
stringer massive
chl-ep-ca chl-ser chl-ca±py sulfide 200 m
sulfide 200 m
Rb/Sr
<0.1 → least altered
0.1-0.5 → weakly altered pXRF results
0.5-1.0 → moderately altered
total measurement 0 1 2 3 0.5 0 5
1.0-2.0 → strongly altered
>2.0 → intensely altered uncertainty (%Gtot)
0 1 2 3 0.5 0 5

Fig. 6. Strip logs for the Ridge zone north (RN18-0224) and the West Block area (BG18-3907 and BG18-3902). Cu and Zn assay results provided by Nyrstar. Alpha-
betical labels correspond to rock photographs provided in Appendix Figure A1. Detailed graphic logs present logged lithology, alteration, and sulfide mineralization.
Abbreviations: ca = calcite, chl = chlorite, ep = epidote, py = pyrite, qtz = quartz, ser = sericite.
451
 452 SCIENTIFIC COMMUNICATIONS
2019), and magnesium, when reported, typically has detection
limits that are too high for optimal use (Fig. 1). In this com-
parison between Rb and Sr measured by pXRF with conven-
tional whole-rock geochemical analyses, we demonstrate that
the Rb/Sr ratio can be used as a robust proxy for the AI.
The similarities in ionic radii, electronegativity, and ioniza-
tion potential of Rb and Sr with K and Ca, respectively (Taylor,
1965) allow their incorporation into K- and Ca-bearing min-
erals. In VHMS hydrothermal systems, Ca- and Na-bearing
primary feldspars and volcanic glass are commonly replaced
by chlorite and K-bearing white mica minerals (e.g., Ishikawa
et al., 1976; Eastoe et al., 1987).
At Myra Falls, the Rb/Sr ratio increases with proximity to
sulfide mineralization. At the Battle orebody, altered foot-
wall andesite of the Price Formation has Rb/Sr ratios >1.0,
whereas felsic volcaniclastic rocks, stratigraphically overlying
zones of sulfide mineralization, have Rb/Sr ratios >2.0 (Fig.
4D). Our pXRF analyses of the same sample set reproduce
the conventional whole-rock geochemical results and effec-
tively replicate the downhole Rb/Sr profile (Fig. 4D).
In the West Block area and Ridge zone north orebody, el-
evated pXRF Rb/Sr ratios, generally >1.5, correspond with
texturally destructive, chlorite- and sericite-rich alteration fa-
cies in footwall andesitic rocks and felsic volcaniclastic host
rocks (App. Fig. A1). Weakly to moderately altered host rocks
have pXRF Rb/Sr ratios <0.75 (App. Fig. A1C, G) and least
altered rocks have pXRF Rb/Sr <0.1 (App. Fig. A1J-L).
The results of this study demonstrate that systematic, in situ
pXRF analysis of drill core can produce robust, on site, and
near-real-time results that can be used to inform drilling and
targeting decisions. The acquisition of pXRF data, compared
to conventional whole-rock geochemistry, is inexpensive, fast,
and adaptable to the desired geochemical output. For exam-
ple, analysis run times can be shorter (~1 min) and completed
on whole core (NQ diameter or greater) depending on the
desired outcome (e.g., Ross et al., 2014a, b, 2016).
The use of Rb/Sr ratio as a proxy for alteration intensity
goes beyond Myra Falls and can be applied to any hydrother-
mal system that results in formation of secondary phyllosili-
cate minerals after feldspar. Additionally, this technique is not
limited to drill core but can also be applied to powdered pulps
and surface samples, which can be used to generate and inter-
pret hydrothermal alteration prospectively maps.
Acknowledgments
This research was carried out as part of a Ph.D. study at
CODES, University of Tasmania. We would like to thank
Nyrstar Myra Falls operation for their financial support and
Rick Sawyer and Armond Stansell for their valuable help. We
would like to acknowledge current and past staff of CODES—
in particular, Jay Thompson, Dr. Sarah Gilbert, and Dr. Ron
Berry—for their assistance with this research. A special thank
you to Dr. Garry Davidson for his contribution at the early
stages of this project. We are grateful to Dr. Pierre-Simon
Ross and Dr. Steve Piercey for providing comprehensive and
constructive comments that improved the manuscript.
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Brian McNulty recently completed his Ph.D.
degree with the Centre for Ore Deposit and Earth
Sciences (CODES) at the University of Tasma-
nia, Australia. His Ph.D. research focused on the
lithostratigraphic architecture and depositional
age of volcanic host rocks of the Myra Falls VHMS
district. Prior to his Ph.D. study, he completed
an M.Sc. degree with the Mineral Deposit Research Unit (MDRU) at the
University of British Columbia, Canada, where he investigated the geology,
alteration, and mineralization of the Niblack VHMS deposit, Alaska. Before
his postgraduate research, he worked in mineral exploration on porphyry and
VHMS projects in Alaska and British Columbia. He currently resides in Van-
couver and is involved with various research projects with MDRU.
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