Groundwater geochemistry and exploration methods: Myra Falls

volcanogenic massive-sulphide deposits, Vancouver Island, British

Columbia, Canada
Graham C. Phipps1, D.R. Boyle & I.D. Clark2
1
Manitoba Water Stewardship, Groundwater Management Section, 200 Saulteaux Crescent. Winnipeg, MB R3J 3W3,
Canada
2
University of Ottawa, Department of Earth Sciences, 140 Louis Pasteur, Ottawa, ON K1N 6N5, Canada

ABSTRACT: The Myra Falls Price deposit is a zinc-rich volcanogenic massive-

sulphide ore-body located in a mountainous region of central Vancouver Island,
British Columbia. High rainfall and steep hydraulic gradients limit the water–mineral
contact, which results in a low solute load in the oxygenated groundwater. Despite
this, significant element contrasts exist that permit the development of groundwater
geochemical methods for exploration. Zinc displays the strongest and most reliable
anomaly contrasts in groundwaters associated with mineralization related to the Price
deposit. Statistical procedures are used to differentiate two overlapping subpopula-
tions of Zn concentrations, which are partitioned into two constituent populations.
A threshold value of 20 µg/l was established, which includes an uncertainty that
allows up to 10% of the background population being defined as anomalous. Zn
anomalies can be further enhanced with a suite of pathfinder elements associated
with primary mineralization and hydrothermal alteration, including Cu, Pb, Cd, Mn,
As, Sb, Ba and U.
In addition to massive-sulphide mineralization, sulphides also exist as clasts within
a breccia unit designated as the ore-clast breccia (OCB). Effective discrimination is
possible between anomalies in groundwaters associated with massive-sulphide
mineralization and groundwaters associated with OCB through the use of elements
associated with primary mineralization and hydrothermal alteration such as K, Rb, B,
Ba, Cd, Sb, U and barite saturation, which are elevated in groundwaters associated
with massive-sulphide mineralization but not the OCB.
Groundwater geochemical exploration methods offer a supplemental tool to
exploration of Zn-rich massive-sulphide deposits where existing infrastructure,
exploration drifts and drill holes are present.
KEYWORDS: groundwater geochemistry; groundwater-based mineral exploration; Zn, Cu, Pb mobility;
Zn-rich mineral deposit; indicator, pathfinder elements; element association; British Columbia, Canada

INTRODUCTION In mountainous terrain with high rainfall and high hydraulic

One of the greatest advantages of using groundwater as a
component within exploration programmes is that once waters
have traversed an ore zone and/or its alteration halo, they are
capable of maintaining a chemical signature of that zone for
some distance from mineralization. The chemical signature will
be characterized by anomalous concentrations of indicator and
pathfinder elements and their differential mobilities may be
useful in determining both the strength and persistence of the
groundwater anomalies. The hydrogeochemical dispersion in
the vicinity of ore deposits should offer a larger exploration
target than lithogeochemical halos. In areas where exploration
drifts and drill holes allow access to groundwater, the use of
groundwater geochemistry will allow a greater use of exist-
ing resources and may also expand the exploration sites by
including water flowing from fractures and faults into the drift.
Geochemistry: Exploration, Environment, Analysis, Vol. 4 2004, pp. 329–340
gradients, the brief contact time between groundwater and
mineralization is expected to lessen element contrasts com-
pared to terrain where longer water–mineral interaction or
acidic waters that are capable of transporting high metal loads
develop. In a review of hydrogeochemical exploration
methods for polymetallic mineral deposits, Miller (1979) pro-
posed that Pb, Zn, Cu, As, Mo, Ni, Ag, Cd, Sb, Se and Be
may act as indicator/pathfinder elements in strongly oxidizing
environments. However, he suggested that the low element
contrasts developed in the conditions described above might
limit the application of hydrogeochemical prospecting
methods.
A detailed hydrogeochemical sampling programme was
undertaken within the Myra Falls volcanogenic massive-
sulphide mining camp of the Buttle Lake Palaeozoic Inlier,
1467-7873/04/$15.00  2004 AEG/ Geological Society of London
330 G.C. Phipps et al.
Vancouver Island, British Columbia (Fig. 1) to determine if
sufficient element contrasts are present and to determine the
most applicable element or suite of analytes for groundwater
geochemical exploration.
SITE DESCRIPTION
Location, physiography and climate
The Myra Falls mining operation is located within the central
Vancouver Island Mountain Ranges, British Columbia, Canada
(4935’N, 12534’W). The mine operation is hosted within the
Buttle Lake Palaeozoic inlier, one of the major Palaeozoic
uplifts on Vancouver Island (Fig. 1); the study area is c. 3000 m
by 3000 m. The topography is mountainous with tree-covered
slopes dissected by stream gulches. Surface drainage consists of
permanent and intermittent streams that tend to follow bedrock
structures. Within the study area the elevation ranges from 200
to 720 m above sea level.
Fig. 1. Location and geological map of
the Buttle Lake uplift, Vancouver
Island, British Columbia. Major Sicker
Group uplifts are outlined on the
location map. The area of this study
which includes the Price
massive-sulphide deposit is outlined on
the geological map.
Mean annual precipitation at Myra Falls exceeds 2500 mm,
most of which falls during the autumn and winter months.
Much of the winter precipitation at the highest elevation falls in
the form of snow, whereas July and August are dry with high
rates of evapotranspiration. Within an adjacent valley (360 m
elevation), the daily temperature ranges from 12 C to 27 C
with a mean value of 8.7 C.
Geological setting
The Sicker Group, exposed locally in the fault-bounded Buttle
Lake uplift, comprises the oldest rocks on Vancouver Island
and represents the known base of the allochthonous Wrangellia
terrane (Jones et al. 1977). The lower three formations of the
Sicker Group – the Price, Myra and Thelwood Formations – are
accessed by surface drill holes and mine workings. The Price
Formation, the oldest of the three, consists of massive basaltic
andesite flows, flow breccias and volcanoclastics. The Myra
 Groundwater geochemistry and exploration methods
Formation is a volcanic and volcanoclastic unit, dominantly
intermediate in composition but ranging from basaltic to
rhyolitic. Minor sedimentary units are present, consisting of
sandstones, siltstones, argillites and chert. The Thelwood
Formation consists of bedded siliceous tuffs, subaqueous
pyroclastics and mafic sills (Juras 1987; Muller 1980). The
volcanogenic massive sulphides in the Myra Camp are
Devonian in age (Juras 1987) and are hosted within the bottom
two of three felsic units in the Myra Formation. Fracture-filled
veining within the camp is dominantly an assemblage of
quartz, chlorite and calcite. The Price, Myra and Thelwood
Formations have undergone greenschist metamorphism, are
mildly to moderately deformed and have moderate to strong
hydrothermal alteration with epidote and chlorite as common
alteration minerals (Pearson 1993; Juras 1987).
Mineralization
Delineated ore bodies within the Myra Falls camp range in size
from 10 000 to 10 000 000 tonne lenses. Sulphide minerals
present in decreasing abundance are pyrite, sphalerite, chalco-
pyrite, galena, tennantite and bornite. Minor amounts of
electrum, stromeyerite, chalcocite and argentite are also present.
Quartz, sericite and barite constitute gangue minerals (Pearson
1993).
The study area is centred around the Price ore-body which is
a small (185 000 tonne), Zn-rich deposit within the middle felsic
unit of the Myra Formation, in the Lynx–Myra–Price (L-M-P)
horizon (Juras 1987). The deposit is located within the Myra-
–Price mountain ridge at an elevation of c. 625 m. Hydrothermal
alteration coeval with massive sulphide mineralization exists
both as discrete cross-cutting zones in the footwall and as
haloes around the ore body and has modified the mineralogical,
textural and chemical composition of the host rock (Juras 1987).
A small feeder/stringer pyrite zone is present beneath the Price
deposit composed of assemblages of quartz, sericite, pyrite and
chlorite. Chlorite-bearing rocks appear on the less intensely
altered fringes (Juras & Pearson 1990; Pearson 1993).
Throughout the mining camp, sulphide clasts of varying sizes
occur within a heterolithic ore clast breccia (OCB) unit.
Although the term OCB is used to describe this unit within the
camp, the prefix ‘ore’ is a misnomer because the OCB is not
ore-grade, but it does aptly describe the incorporation and
dilution of previous ore deposit sulphides in a proximal slump
or explosive breccia. The OCB consists of volcanoclastic
submarine debris flows and minor submarine pyroclastics. Clast
compositions span a wide range of lithologies and include chert,
argillite, rhyolite, dacite, andesite and mafic compositions,
together with massive-sulphide clasts, which are dominantly
pyritic composition. Rhyolite olistoliths are typically mineralized
with disseminated pyrite and occasionally massive sulphides.
The OCB unit contains little or no phyllosilicate minerals, and
lacks the alteration halo normally present around the volcanic
hosted primary ore. It also lacks massive barite, although barite
may be present with the sulphide clasts (Pearson 1993; Juras
1987).
The presence of the OCB presents a major problem in
developing groundwater geochemical exploration methods in
this mining camp. The differentiation of groundwater geo-
chemical anomalies related to economic massive sulphide as
compared to those related to the OCB is considered paramount
in developing a groundwater geochemical exploration method.
Whole-rock analyses of the mine sequence rock units are
presented in Table 1. Potential indicator elements include Zn,
Cu and Pb, with potential pathfinder elements Ba, U, Se and Sb
enriched in the ore zone. Arsenic is enriched not only in the
331
Price ore zone, but also in pyritiferous argillaceous sediments in
this setting.
Hydrogeology
Late-stage faults have the greatest lengths of structures in the
camp and may be the most permeable component within the
Price area. These late extensional faults control stream positions
overlying the Price ore-body (Hamilton 1993). Streams in the
immediate vicinity of the exploration drifts have intermittent
flow at the valley elevation and many of the streams when
observed at various locations over their length appear to be
losing streams. Most recharge within the mountain core is likely
contributed directly from the streams. The steep topography
will lead to high groundwater gradients and groundwater flow
will primarily be vertical or subvertical within the mountain
ridge.
A greater proportion of the water entering the exploration
drifts is observed within the carapace of the mountainside
where a greater degree of fracturing and weathering is expected.
Within the inner core of the mountain groundwater flow into
the Price drifts is characterized by sections of drift of varying
width containing water-bearing fractures or faults which typi-
cally have low flows, separated by dry sections composed of
competent rock. Similar heterogeneity within the rock overlying
the drifts would lead to discrete zones of groundwater flow.
Oxidizing conditions in groundwaters circulating through
mineral deposits will mobilize soluble elements from the ore
and alteration lithologies. Increased fracturing, shearing and
foliation in zones affected by hydrothermal alteration will act as
conduits for groundwater flow and increase the contact surfaces
for water to react in these zones. The resulting water–rock
interaction should impart a distinctive chemistry to the waters.
METHODOLOGY
Field methods, sample collection and analytical
techniques
Surface waters were collected from permanent and temporal
streams (n = 24) and from seeps and springs (n = 13).
Groundwaters (n = 188) were sampled from flowing drill holes,
and wet fractures and faults accessed by four exploration drifts
originating on the valley side at 238 m, 416 m, 580 m and 626 m
elevations (Price 13, 9, 5 and 4 levels, respectively). Most drill
holes were arranged in a fan-style orientation that radiated out
in a vertical array from drilling stations located at c.15 m
spacing. Drill holes intersecting the Price ore-body were
accessed from the 4 and 5 levels. Drill holes intersecting the
OCB unit were accessed from 9 level.
On-site measurements consisted of water temperature, pH,
platinum electrode oxidation–reduction potential (Eh), dis-
solved oxygen (DO) and electrical conductance (EC). Waters
were pressure filtered at 0.45 µm at the time of sampling.
High-density polyethylene sample containers were pre-leached
for a minimum of one month with de-ionized water and then
rinsed with a sample aliquot which was disposed prior to filling
the container. A sample for major cation and trace element
analyses was preserved with ultra-pure nitric acid (2% by sample
volume). Samples were refrigerated until analysed at the Geo-
logical Survey of Canada Laboratory. Total alkalinity was
measured by titration; anions were determined by ion chroma-
tography. The following techniques were used: ICP-OES for Si,
Ca, Mg, Fe, B, Sr, Sc, Ti, Mo; ICP-MS for Rb, Cs, Be, Mo, Ag,
As, Sb, Se, U, Ga, Tl, In, Hg, Bi; and, both ICP-OES and
ICP-MS for Al, Ba, V, Cr, Ni, Co, Mn, Zn, Cu, Pb and Cd.
 332

Table 1. Median whole rock composition for rock units of the Sicker Group in the Price area.

Description Massive H-W H-W H-W H-W Ore-clast Lower Upper L-M-P Massive L-M-P G-flow Upper Upper
sulphide rhyo- argilllite QFP hanging- breccia mixed dacite (rhyo/qtz- sulphide hanging- unit mixed mafic
(H-W) dacite wall (OCB) volcano- sericite- (Price) wall volcano- unit
andesite clastics schist) clastics
No. analyses 8 17 3 2 22 43 10 20 5 7 12 2 15 7
wt %
SiO2 1.4 68.3 78.5 69.8 50.2 58.1 55.6 58.0 60.4 12.2 60.6 43.8 53.4 49.1
Al2O3 0.3 14.2 5.8 13.2 16.7 14.7 16.5 16.3 16.2 3.3 14.6 12.1 16.6 15.2
Fe2O3 54.6 5.1 3.4 3.0 9.9 6.7 8.3 7.2 6.1 43.3 5.9 9.5 8.0 10.0
MnO 0.01 0.04 0.03 0.06 0.16 0.11 0.12 0.12 0.04 0.02 0.08 0.2 0.1 0.2
MgO 0.06 1.48 1.53 1.14 4.77 2.67 3.56 3.11 1.05 0.5 2.12 12.2 3.12 3.35
CaO 0.185 2.89 2.33 3.66 7.94 5.19 5.255 4.56 2.69 0.8 4.64 10.5 5.9 6.81
Na2O 0.075 0.9 0.3 3 2.55 2.1 2.5 3.85 0.37 0.145 2.7 1.5 3.4 0.8
K2O 0.05 3 1.42 2.015 0.43 1.34 1.99 1.04 3.96 0.87 1.6 0.0525 1.14 1.69
CO2 0.4 1.8 3 2.75 2.35 1.9 3.65 2.2 2.1 1.4 2.6 4.7 1.9 2
P2O5 0.02 0.1 0.1 0.09 0.155 0.15 0.285 0.2 0.21 0.02 0.14 0.155 0.22 0.12
S 46.05 0.09 0.37 0.06 0.02 0.35 0.37 0.02 3.36 37.1 0.01 0.01 0.04 0.01
ppm
Ba 3650 1700 1500 1200 335 940 665 590 1700 8600 820 270 730 700
Co 2.5 2.5 2.5 3.8 23.0 13.0 14.5 11.0 9.0 10.0 9.5 43.5 14.0 28.0
G.C. Phipps et al.

Cr 5.0 5.0 40.0 7.5 38.0 12.0 30.5 8.0 17.0 5.0 19.5 1300 23.0 140
Cu 69000 33 42 30 47 60 54 22 26 27000 5 83 54 30
Ni 29 5 55 5 16 5 5 5 5 32 30 275 13 61
Sr 29 150 61 195 370 250 205 370 86 71 380 210 320 180
V 36 45 200 46 230 130 125 94 52 46 59 210 140 190
Zn 7000 82 240 74 8 200 92 95 160 6200 74 82 110 98
Mo 155 1.6 13.0 0.35 0.5 1.6 0.9 0.55 2.3 64.0 0.35 0.3 0.65 0.3
Pb 240 13.0 21.0 29.0 4.0 30.0 7.5 5.5 37.0 520 4.0 2.5 6.0 5.0
Rb 0.9 53.0 29.0 35.0 7.2 21.0 40.5 18.5 60.0 12.0 37.0 0.8 20.0 41.0
U 1.4 1.3 3.9 1.2 0.4 1.1 1.1 1.1 1.3 4.7 1.0 0.4 1.3 0.3
No. analyses
8 6 3 2 8 13 3 6 4 2 6 2 7 4
(B, As, Se, Sb)
B <10 18 15 14 <10 <10 13 <10 30 13 <10 <10 <10 <10
As 245 16 150 6 3.5 20 9 2 20 350 <2 3 3 4
Se 17 <5 <5 <5 <5 <5 <5 <5 <5 30 <5 <5 <5 <5
Sb 18.0 0.75 1.7 0.9 1.05 3 0.6 1 3.4 28.0 0.65 0.55 0.7 0.7
 Groundwater geochemistry and exploration methods 333

Fig. 2. Analytical results summarized

for all samples showing the full range
of results (bars) and the interquartile
range (shaded boxes). Units: pH,
standard units; DO, mg/l; Eh, V; EC,
log µS/cm; all other parameters are log
mg/l, or µg/l, as noted.

Table 2. Detection limits, recode (below detection values) and
values, and summary statistics for surface and ground water chemical parameters. Concentrations are in µg/l except where
noted. See text for methods used in determining recode values for <D.L. and
values.

Surface waters (n=37) Groundwaters (n=188)

Analyte Detection Recode Power Min. Median Max. Min. Median Max.
limit value a transformation

value b
Temp (oC) – –
0.75 7.6 11.5 19.0 5.8 6.7 11.9
EC (µS/cm) – – 0.05 50 140 307 76 198 782
pH – –
0.90 6.1 7.3 7.9 6.4 7.5 9.6
Eh (V) – – 3.15 0.36 0.41 0.52 0.11 0.41 0.48
DO (mg/l) – – 1.35 5.7 10.1 12.2 0.8 9.6 18.3
SiO2 (mg/l) 0.01 as Si – 0.25 1.1 3.4 4.9 0.9 5.3 12
Ca (mg/l) 0.005 – 1.30 2.4 25 38 2.4 37 72
Mg (mg/l) 0.002 – 0.20 0.14 0.71 2.7 0.02 1.7 12.0
Na (mg/l) 0.02 –
0.10 0.052 0.77 2.0 0.31 2.0 160
K (mg/l) 0.02 0.01 0.35 0.01 0.029 0.17 0.01 0.25 1.7
HCO3 (mg/l) – 2.00 6.9 73.9 115 18.3 115 177
SO4 (mg/l) 0.05 – 0.00 0.46 0.94 15 0.66 12.1 286
Cl (mg/l) 0.05 –
0.45 0.25 0.44 0.75 0.21 0.82 10
Al 0.5 0.48
0.40 4.6 8.4 55.5 0.48 4.2 40
Fe 3 1.65
0.05 1.65 4.0 22 1.65 9.0 160
Li 1 0.13
0.85 0.13 1.0 2.0 0.13 1.0 79
Rb 0.2 0.003 0.60 0.003 0.003 0.2 0.003 0.003 0.8
Sr 0.03 – 0.15 4.9 20 180 25 410 6550
Ba 0.5 – 0.30 1.0 5.4 63 8.4 77 380
B 16 3.0 0.00 3.0 3.0 49 3.0 3.0 2900
V 0.5 0.07
0.30 0.07 0.07 0.89 0.07 0.07 4.7
Cr 0.2 0.06 0.30 0.06 0.06 0.7 0.06 0.06 3.0
Ni 1 0.3 0.10 0.3 0.3 0.69 0.3 0.3 7.6
Co 0.2 0.01
0.05 0.01 0.01 0.05 0.01 0.01 1.4
Mn 0.2 0.18
0.20 0.18 0.36 2.9 0.18 1.3 110
Mo 0.5 0.01 0.60 0.01 0.01 0.69 0.01 3.1 20
Zn 2 0.44 0.00 0.44 3.8 17 0.44 5.0 1400
Cu 0.5 0.23
0.15 0.23 0.23 1.8 0.23 0.96 40
Pb 0.2 0.15
0.80 0.15 0.15 1.3 0.15 0.34 34
Cd 0.5 0.24
1.45 0.24 0.24 0.24 0.24 0.24 12
As 1 0.58 0.10 0.58 0.58 0.58 0.58 5.1 67
Sb 0.2 0.15
0.30 0.15 0.15 0.85 0.15 0.87 130
Se 2 1.25
0.60 1.25 1.25 3.0 1.25 1.25 12
U 0.2 0.07 0.10 0.07 0.07 0.07 0.07 0.3 6.7

Data for NO3, NO2, F, Br, Cs, Be, Sc, Ti, Ag, Ga, In, Hg and Tl not included.
aa
For samples below detection.
bb
Box & Cox (1964) power transformation (Ln transformation for
=0)

RESULTS Dissolved oxygen (DO) is present in all waters; surface waters

The maximum, minimum and range of the 25th to 75th
percentiles are presented for analytical results in Figure 2.
Median concentrations for analytes in surface water and
groundwater are presented in Table 2. The concentrations of
NO2, NO3, F, Br, Rb, Cs, Be, B, Se, Sc, Ti, Va, Cr, Co, Ni, Ga,
Ag, Cd, In, Hg, Tl and Bi were below the limit of detection for
the majority of waters.
Dissolved oxygen, redox, electrical conductivity and pH
conditions
Redox (Eh) values range from 0.11 to 0.52 V. Median Eh values
are similar for both surface and ground waters at 0.41 V.
have a median value of 10.1 mg/l, which is approximately
at saturation with respect to atmospheric oxygen for field
conditions. Groundwaters have greater variability ranging from
0.8 to 18 mg/l, with a median value of 9.6 mg/l. The majority
of the waters are moderately to highly oxidizing indicating that
oxygen-consuming reactions have not gone to completion in
these recently recharged waters.
Electrical conductivity (EC) is quite low for both surface
water and groundwaters: median values of EC are 140 and
198 µS/cm for surface water and groundwaters, respectively.
The maximum EC for groundwater is 780 µS/cm. The estimate
of total dissolved solids (TDS) from concentration data of the
334 G.C. Phipps et al.
Fig. 3. Trilinear diagram of major ions showing major chemical
proportions (% milli-equivalence) of groundwater and surface water
samples. Greater proportions of Na indicate Ca ⇒ 2Na exchange.
Dominant anions in groundwaters trend from HCO3
to SO42
as
recharge waters react with sulphides.
interquartile range is relatively low for a mineralized environ-
ment and ranges from 150 to 200 mg/l, which is considered
well within the range of ‘fresh’ groundwater.
The pH values range from 6.1 to 9.6, with near-similar
median values of 7.3 and 7.5 for surface water and ground-
waters, respectively. The pH in most waters spans a very narrow
range with the central 50th percentile values spanning 6.4 to 7.8
standard units. The log PCO2 in groundwater from Price 4 and
5 levels averages 2.5, and these waters are near saturation with
respect to calcite. The prime controls on the pH of these waters
is likely the elevated CO2 in the recharge which is then buffered
by reacting with the ubiquitous calcite-lined fractures and to a
lesser extent the consumption of H+ during weathering of
silicate minerals.
Surface water chemistry
Surface water chemistry is dominated by Ca2+ and HCO3

(Fig. 3), and has low dissolved solids as indicated by the EC.
Median values for all major ions are lower in surface waters than
in groundwaters (Table 2). The maximum concentration of
SO42
is 15 mg/l, which is only slightly greater than the
median groundwater concentration of 12 mg/l. The median
SO42
concentration of surface waters (0.94 mg/l) closely
reflects the local rainfall concentration (0.91 mg/l), indicating
little interaction between most surface waters and sulphur-
containing minerals or contribution of SO42
from base-flow
discharge. Median Cu and Pb concentrations in surface waters
are below detection and maximum values of these elements are
very low, 1.8 and 1.3 µg/l for Cu and Pb, respectively. Median
concentrations for the remainder of the trace metals in the
surface aqueous environment are below detection, with the
exception of Zn and Mn. Zinc concentrations are somewhat
higher than Cu or Pb, and median Zn concentrations in surface
waters (3.8 µg/l) are only slightly less than in groundwaters
(5.0 µg/l). Two surface waters sampled on the upper Price
hillside in close proximity to the Lynx–Myra–Price horizon
have Zn concentrations of 13 and 17 µg/l and may indicate
contact with mineralization.
The surface water environment largely reflects element
chemistry derived from meteoric precipitation. A few waters
indicate minor interaction with minerals or limited contribution
from base-flow discharge. Median concentrations of solutes in
surface water are likely to be very representative of the
chemistry of groundwater recharge.
Groundwater chemistry
The major cation composition of most groundwater is domi-
nated by Ca2+ with only a minor contribution from Mg2+.
Waters trend toward Na+ with a smaller cluster of waters
characterized by Na+ as the dominant cation (Fig. 3). Anion
composition is primarily dominated by HCO3
with a trend
towards SO42
dominant waters in a minority of waters. The
chemistry of many groundwaters reflects little interaction with
rocks other than contact with quartz–chlorite–calcite lined
fractures. These waters are dominated by Ca2+ – HCO3

chemistry and have very similar chemistry to surface (recharge)
waters, but with a slight increase in Ca2+ and HCO3

concentrations and EC. The proportion of Na+ increases in
groundwaters towards the central core of the mountain where
groundwaters have travelled through a greater thickness of
rock, have a greater residence time, and where evidence
suggests Ca2+ Na+ exchange has occurred. Sources of dissolved
sulphate include SO42
in recharge waters and oxidation of
disseminated and massive sulphides. Sodium-dominated
groundwaters have a higher proportion of anions as SO42
.
Nine groundwaters have estimated TDS greater than
300 mg/l: all of these are sulphate or sodium sulphate
dominated groundwaters. The remainder have estimated TDS
less than 300 mg/l, which illustrates the low mineral content of
groundwater in this setting.
The concentrations of ore-forming metals (Zn, Cu and Pb) in
groundwaters show large concentration contrasts. Zinc concen-
trations span over three orders of magnitude with a maximum
concentration of 1400 µg/l (Table 2), even though the median
groundwater Zn concentration of 5 µg/l is only slightly greater
than the median concentration in surface waters. Copper and
Pb concentrations in groundwater have median values of 0.96
and 0.34 µg/l, but maximum concentrations of 40 and 34 µg/l
for Cu and Pb, respectively.
Concentrations of trace elements associated with the Price
ore such as Cd and Se are moderately to heavily censored by
values below the detection limit (Table 2). Cadmium levels tend
to be above detection level only when Zn concentrations are
greater than 50 µg/l, although not all waters with high Zn
rigidly conform to this observation. Arsenic and Sb concen-
trations in groundwater have fewer censored values than the
other trace metals and Ba is present in all groundwaters. Metals
associated with mafic units including V, Cr, Ni and Co, are
highly censored in the groundwater environment. Maximum
concentrations of these elements are quite low and range from
1.4 to 7.6 µg/l.
Statistical analyses
Statistical analyses allow for the formulation of robust methods
in determining element distributions and correlations, and
where more than one population is present these methods allow
for the disaggregation of data into separate populations. These
techniques aid in the interpretation of anomalous populations
and in developing threshold values.
Histograms and probability plots were prepared for each
variable showing that all variables are skewed to some degree.
Variables were transformed into Gaussian distributions using
the generalized power transform methods of Box & Cox (1964)
in the form:
 Groundwater geochemistry and exploration methods
(x

1)
y= (
[0)


and
y=ln(x) (
=0)
where x is the original concentration, y is the transformed value
and
is a chosen value to minimize skewness and kurtosis.
Minimizing asymmetry within each variable may introduce a
highly peaked distribution; therefore
is incrementally adjusted
using the weighting scheme that included kurtosis (K) and
skewness (S) of the data as suggested by Howarth & Earle
(1979) to achieve a minimum value of F in the function:
F=2|S|+|3
K|
The values below detection were recoded to minimize the effect
from the censored data on further statistical procedures. It was
assumed that the values above and below the detection limit for
each analyte followed the same normal population distribution
calculated in the above procedure. The values below detection
were recoded by accounting for their percentile ranking along
the cumulative probability curve and using the central censored
point, the corresponding value from the transformed concen-
trations was assigned as the recode value. Detection limits,
recode values,
and median values for select elements and
variables of interest are shown in Table 2.
Element associations
Table 3 shows correlation coefficients between transformed
parameters in groundwaters. The ore-forming elements, Zn, Cu
and Pb, have high correlation coefficients with each other. Zinc
is also highly correlated to Mn, Cd, Sb and U. All of these
elements except Mn are concentrated in Price massive sulphides
(Table 1). Cadmium, Sb and U, and to a lesser extent Se, are
positively correlated with Zn. Copper and Pb tend to have
lower correlations with ore-accessory elements. Correlation
coefficients between SO42
and ore-forming and ore-accessory
elements are low.
Potassium, Rb and B have a very high correlation amongst
themselves and represent elements associated with alteration
zone mineralogy.
Dissolved As has a weak correlation with Zn, Cu, Cd and Se,
elements that originate from mineralization. In addition to the
mineralized zone, As is also concentrated in argillaceous sedi-
ments in this environment and therefore is more dispersed.
Arsenic may be more useful as a pathfinder in reconnaissance-
scale groundwater geochemical programmes than in the local
scale used in this study.
Zinc mobility and threshold estimation
Filtration studies of selected groundwaters associated with the
Price deposit carried out concurrent to this study (Phipps et al.
1997) show that of the ore indicator elements, only Zn is
predominantly transported as a dissolved species. Adsorption
to suspended particles, which are dominantly amorphous
Fe-hydroxides that are greater than 0.45 µm in size, is relatively
high for Cu and Pb. The results of that work showed that 40 to
50% of the total Cu in HCO3
and SO42
dominated waters
and that 70 to 80% of the Pb is transported sorbed to particu-
lates greater than 0.45 µm. In contrast, median sorption losses
of Zn to suspended solids is c. 10% and 5% of the total Zn
concentration in HCO3
and SO42
waters. Particulates are
expected to settle or be filtered out of solution during transport,
335
whereas elements transported in predominantly dissolved form
will have a greater dispersion in the groundwater. The greater
mobility of Zn in oxidizing groundwaters in contact with
sulphide mineralization has been shown by many authors (e.g.
Cameron 1978; Giblin 1978; Laville-Timsit & Wilhelm 1989).
Precipitation of secondary minerals will limit the concen-
tration of Zn in solution. Mann & Deutscher (1980) investi-
gated the most probable Zn phases to precipitate in various
solution matrices. The first phase to precipitate in bicarbonate
and sulphate waters with pH values between 6 and 8 is
smithsonite (ZnCO3). Groundwaters in this study were not
saturated with respect to smithsonite or other common Zn
minerals as calculated using the speciation program PHREEQC
(Parkhurst 1995) and the geochemical data base of WATEQ4F
(Ball & Nordstrom 1991). Other than slight losses by sorption
to Fe-hydroxides, Zn would be expected to remain in solution.
Because Zn is a major constituent of the ore deposit and
remains in solution once dissolved, it is an excellent ore
indicator element in groundwater.
In geochemical surveys it is assumed that both background
and anomalous populations are adequately represented in the
data set. Estimating the maximum background or non-
mineralized concentration below the anomaly threshold value is
the greatest problem encountered in exploration data analyses.
Although there is no single, widely accepted method of
threshold estimation, subjective cut-off values such as mean
plus two or three standard deviations (SD) would be unsatis-
factory in an area of known mineralization where anomalous
waters would be expected to account for more than a very small
proportion of the population. Disaggregating or partitioning
data sets into constituent populations for grouping of data sets
and for estimating threshold values has been successively
demonstrated by Sinclair (1974, 1976, 1991) as an aid in
geochemical data analyses.
The probability plot (Fig. 4) of natural log (ln) transformed
groundwater Zn concentrations reveals two populations with an
inflection point which divides the data set into 82% and 18%
proportions. Converting the idealized populations to µg/l, the
median and
1 SD, +1 SD concentrations are 3.6, 1.0 and 13
for population A, and 178, 61 and 520 for population B.
The two subpopulations are recombined at their respective
proportions and selected points are replotted with the original
data which shows that there is a very good fit between the data
(Fig. 4).
Whereas there is good separation between the median  1
SD concentrations from transformed values, there is consider-
able overlap between the two populations. This can be expected
from groundwaters in close proximity to massive-sulphide
mineralization, where some ore minerals are disseminated
outside of the massive mineralization (see Zn concentrations
for various rock units in Table 1) and groundwater mixing may
occur. The result is an overlap of the two Zn populations and
therefore a degree of uncertainty must be expected in assigning
a threshold value. The degree of uncertainty will decrease as
the threshold value is raised. Based on the two constituent
populations of Zn there would be approximately 10% of the
cumulative population A above a threshold of 20 µg/l Zn. This
value drops to 5% and 1% as the threshold value is raised to 25
and 38 µg/l. By raising the threshold there is less chance of
assigning a background Zn concentration as anomalous but
with the consequence of not recognizing some true anomalous
waters. The threshold value chosen should to be based on
the acceptable risk of uncertainty (or confidence). Therefore
a threshold value of 20 µg/l Zn is selected to allow for
an acceptable risk (10%) of assigning background waters as
anomalous.
 336

Table 3. Pearson product moment correlation coefficients for transformed concentrations of analytes in groundwater (n=188) Zinc correlation coefficients are highlighted because Zn is the predominant ore metal and is the most mobile of the ore forming elements.

pH Eh DO SiO2 Ca Mg Na K Al Fe HCO3 SO4 Cl Li Rb Sr Ba B V Cr Ni Co Mn Mo Zn Cu Pb Cd As Sb Se U

EC 0.21
0.30
0.26 0.56 0.38 0.22 0.67 0.54
0.17 0.13 0.43 0.72 0.65 0.18 0.35 0.50 0.25 0.48 0.01 0.00 0.19 0.02 0.23 0.56 0.11 0.11 0.29 0.13 0.40 0.32 0.06 0.22
pH 1.00
0.27
0.10 0.24
0.25
0.13 0.38 0.13 0.12
0.12
0.23 0.30 0.16
0.01 0.13 0.08
0.09 0.25
0.01
0.16
0.04 0.09 0.03 0.23
0.12
0.06 0.00
0.13 0.11 0.07 0.06
0.01
Eh 1.00 0.33
0.33 0.03 0.05
0.41
0.29
0.06
0.21
0.01
0.36
0.35
0.12
0.26
0.21
0.10
0.32 0.13 0.10
0.13 0.05
0.32
0.30 0.00
0.04
0.19 0.02
0.25
0.06 0.07 0.02
DO 1.00
0.27
0.28
0.08
0.22
0.22 0.21
0.23
0.35
0.15
0.26 0.16
0.04
0.21
0.29
0.01
0.03 0.05
0.31
0.07
0.22
0.22
0.15
0.11
0.30
0.17
0.31
0.22
0.21
0.29
SiO2 1.00 0.10 0.39 0.79 0.65
0.14 0.11 0.28 0.57 0.64 0.24 0.45 0.63 0.31 0.56 0.05 0.00 0.14
0.01 0.28 0.60
0.04
0.05 0.24 0.02 0.58 0.28 0.12 0.24
Ca 1.00 0.43
0.10 0.12
0.34 0.19 0.86 0.11 0.23
0.09
0.11 0.28 0.52
0.35 0.03 0.26 0.26 0.13 0.09 0.03 0.30 0.27 0.30 0.26 0.19 0.37 0.16 0.31
Mg 1.00 0.17 0.60
0.37 0.13 0.60 0.21 0.38 0.08 0.46 0.74 0.50 0.08 0.06 0.17 0.19
0.03 0.32 0.29 0.22 0.18 0.27 0.20 0.45 0.51 0.18 0.63
Na 1.00 0.70
0.07 0.11 0.08 0.77 0.61 0.29 0.58 0.66 0.12 0.78 0.01
0.19 0.17 0.00 0.31 0.75
0.10
0.01 0.20
0.05 0.60 0.28 0.00 0.15
K 1.00
0.26 0.21 0.36 0.65 0.64 0.19 0.79 0.87 0.34 0.62 0.05 0.04 0.34
0.01 0.47 0.70 0.15 0.22 0.36 0.11 0.73 0.49 0.07 0.50
Al 1.00 0.18
0.38
0.10
0.29 0.23
0.17
0.34
0.36 0.08 0.01
0.21
0.08
0.04
0.04
0.11 0.05
0.01 0.04
0.06
0.22
0.29
0.10
0.30
Fe 1.00 0.23 0.20 0.21 0.13 0.11 0.22 0.24 0.07
0.16 0.10 0.13
0.21 0.41 0.15 0.16 0.20 0.42 0.21 0.26 0.19
0.12 0.19
HCO3 1.00 0.14 0.45
0.02 0.12 0.48 0.62
0.14 0.05 0.31 0.32 0.03 0.18 0.12 0.23 0.26 0.37 0.26 0.32 0.40 0.13 0.41
SO4 1.00 0.52 0.28 0.50 0.65 0.11 0.63
0.10
0.26 0.17 0.10 0.43 0.82 0.19 0.20 0.30 0.14 0.63 0.47 0.15 0.29
Cl 1.00 0.15 0.46 0.60 0.44 0.47 0.01 0.23 0.27
0.08 0.41 0.47 0.06 0.08 0.37 0.16 0.47 0.31 0.01 0.32
Li 1.00 0.18 0.21
0.11 0.37
0.20
0.10
0.02
0.22 0.18 0.31 0.01
0.07 0.19 0.00 0.20 0.05
0.02 0.04
Rb 1.00 0.68 0.06 0.63 0.07
0.06 0.24
0.04 0.36 0.56 0.07 0.07 0.15
0.07 0.56 0.26
0.07 0.33
Sr 1.00 0.47 0.52 0.03 0.01 0.26 0.01 0.47 0.71 0.13 0.19 0.34 0.10 0.75 0.63 0.12 0.58
Ba 1.00
0.18
0.02 0.44 0.30 0.09 0.37 0.13 0.21 0.30 0.40 0.27 0.36 0.48 0.20 0.43
B 1.00 0.03
0.25 0.11
0.11 0.28 0.64
0.13
0.14 0.07
0.17 0.45 0.07
0.16 0.01
G.C. Phipps et al.

V 1.00 0.04 0.17 0.25
0.11
0.05 0.01 0.00
0.06
0.02
0.02 0.07 0.10 0.11
Cr 1.00 0.23 0.02 0.01
0.25 0.05 0.11 0.08 0.14
0.07 0.03 0.02 0.12
Ni 1.00 0.30 0.26 0.18 0.27 0.31 0.24 0.26 0.26 0.22 0.06 0.23
Co 1.00 0.08 0.05 0.22 0.18 0.04 0.10 0.11 0.15 0.23 0.11
Mn 1.00 0.42 0.43 0.37 0.48 0.37 0.49 0.44 0.07 0.38
Mo 1.00 0.17 0.22 0.31 0.12 0.78 0.60 0.20 0.44
Zn 1.00 0.63 0.59 0.60 0.22 0.40 0.29 0.39
Cu 1.00 0.47 0.50 0.25 0.47 0.25 0.40
Pb 1.00 0.44 0.38 0.41 0.17 0.42
Cd 1.00 0.14 0.38 0.27 0.37
As 1.00 0.68 0.14 0.55
Sb 1.00 0.43 0.74
Se 1.00 0.43
U 1.00
 Groundwater geochemistry and exploration methods
Fig. 4. Probability plot of groundwater Zn partitioned into two
constituent populations. Original data (x) and recombined ideal
mixture of partitioned populations (o) plot in very good agreement.
The inflection point between the two populations is at 0.82 cumu-
lative probability.
Applications to exploration
Groundwater chemical data (Table 4) are presented for two
sections intersecting the Price ore-body 150 m apart. The data
illustrate element contrasts between background and anomalous
groundwaters draining this ore-body and its surrounding rock
units (Fig. 5). Water emanating from drill holes located above
mineralization display background chemistries (water from drill
holes Pr4-54, Pr4-36 and Pr4-35 on section 51+50m E, and
Pr4-103 and Pr5-74 on section 50+00m E). The groundwaters
with background chemistry (e.g. Pr4-35 and Pr4-36) have
concentrations of major ions (i.e. SO4, SiO2, Na) similar to
surface water values (Table 2), and have therefore undergone
little rock interaction following recharge.
In the Price area, the high DO conditions oxidize dissolved
Fe, derived predominantly from pyrite, producing Fe3+, which
is rapidly removed from solution in the form of oxy-hydroxides.
At this location the Fe-hydroxides have been shown to prefer-
entially remove Pb > Cu > Zn from solution by adsorption and
co-precipitation (Phipps et al. 1997). Oxidation of economic
mineralization with a low ratio of pyrite to ore minerals will
result in a greater proportion of pathfinder elements remaining
dissolved and being transported in water because of the
lower losses to sorption and co-precipitation as Fe-hydroxides
precipitate. This is consistent with higher Cu and Pb con-
centrations observed in anomalous groundwater with lower
Fe concentrations (Table 4). Increased concentrations of
indicator/pathfinder elements in the groundwater at closer
proximity to the ore may provide multi-element support for the
Zn anomaly. As the flow path distance from the ore increases,
the intensity of this enhancement is expected to lessen as Cu
and Pb are preferentially removed from solution as compared to
Zn.
In waters sampled from boreholes shown in Figure 5, the Zn
concentration reaches maximum values of 1100 and 1400 µg/l
(Table 4), in contrast to those from adjacent sampling sites with
concentration <10 µg/l. In anomalous groundwaters the con-
centration of associated pathfinders (Cu and Pb) and indicators
(e.g. Cd, Sb, Mn, As and U) can be used as multi-element
support for the Zn anomaly.
Uranium, As and Sb, which are enriched in the ore, tend to
be slightly elevated in anomalous waters (Table 4). These
elements, in conjunction with other pathfinders and indicators,
are useful in further anomaly definition. Copper, Pb, Cd and Sb
show enrichments in groundwaters with anomalous Zn con-
centrations in both sections, although this is not always the case
337
in other groundwaters from the Price area. Strontium is elevated
in most groundwaters from these sections. This most prob-
ably reflects its elevated concentrations in hanging-wall rocks
(Table 1). Lithium, Rb, B and Mo concentrations, although
variable, tend to be higher in groundwaters at 50+00m E as
compared to those at 51+50m E. Groundwaters at section
51+50m E also tend to have higher Ba concentrations than
those at 50+00m E. Rubidium and B are associated with
alteration mineralogy and the higher concentrations in back-
ground water at 50+00m E may show promise of identifying
alteration and the proximity to the ore. This illustrates that not
all groundwaters interacting with ore and alteration minerals will
have the same suite of enhanced elements.
Elements with a basic rock affinity (V, Cr, Ni and Co) are
often elevated in groundwaters draining areas underlying the
mafic G-flow unit in the Price area and they may be effective
indicators for groundwater contact with mafic rock. Manganese,
although not concentrated in the ore (Table 1), is elevated in
most of the anomalous waters (Table 4). The origin of Mn is
also most probably from the overlying mafic unit.
Saturation indices may also be beneficial in support for the
detection of anomalous water. Of the common gangue and
alteration minerals present (chlorite, sericite/muscovite and
barite) only the saturation indices of barite offer an opportunity
to be potentially useful as an indicator of the presence of altera-
tion zones or primary mineralization. Groundwater with rela-
tively high Ba concentration and saturated with respect to barite
may be indicative of proximity to primary alteration or ore.
In summary, Zn is a definitive indicator element due to its
superior mobility in the groundwater environment. Other
indicators and pathfinder elements (Cu, Pb, Cd, Mn, As, Sb, U
and barite saturation index) may enhance the Zn anomalies and
give some indication of proximity to ore.
Discrimination between massive-sulphide mineralization
and ore clast breccia (OCB)
Summary statistics for groundwaters with Zn d 20 µg/l in the
vicinity of the Price ore-body (levels 4 and 5) (n = 30) and from
the OCB unit (n = 7) are outlined in Table 5. Ore-forming
elements (Zn, Cu and Pb) are not definitive as discriminators
between the two types of mineralization since both types of
mineralization contain similar sulphide minerals. Median values
of K, Rb, B, Sr and Mg (sericite/muscovite, feldspar and
chlorite origin) are significantly greater in waters associated with
the Price deposit as compared to the OCB. Barium, Cd and Sb
are the only ore-related pathfinder elements that have a much
greater median and maximum concentration in groundwaters
related to the Price deposit. Chromium in groundwater associ-
ated with the Price deposit is present in very low concentrations
but significantly greater than in groundwater from the OCB.
Although Cr is not present in the ore or host rock, chromite is
present above the hanging-wall of the Price ore-body (Juras
1987), but this mineral should be resistant to chemical attack.
However, Boyle (1974) reports that Cr is sometimes present as
chrome-mica in alteration zones associated with polymetallic
sulphide deposits, and weathering would release Cr to the
groundwater.
The elevated Ba concentrations in the Price waters are most
probably related to the higher barite concentration within the
Price ore and host rocks and possibly from Ba from alteration
minerals. Barium and SO42
in these waters have an inverse
relationship in groundwater resulting from barite solubility
control. A greater number of waters associated with the Price
deposit are above saturation with respect to barite as compared
to water in contact with the OCB.
 338

Table 4. Chemistry of groundwaters associated with the Price ore body environment for sections 51+50 and 50+00 E (mine coordinates). This data corresponds to sampling sites on Figure 5. Concentrations are in ppb except where noted (<D.L.=less
than detection).

Section 50+00m E Section 51+50m E

Background Anomalous Background Anomalous
Analyte Pr4-103 Pr5-74 Pr5-76 Pr5-75 Pr4-105 Pr4-104 Pr4-106 Pr5-73 Pr4-54 Pr4-35 Pr4-36 Pr4-34 Pr4-32 Pr5-80 Pr5-81
o
Temp ( C) 7.5 6.9 6.5 6.3 7.5 7.2 6.5 6.7 5.9 6.1 6.0 6.1 7.0 6.3 6.3
EC (µS/cm) 186 181 189 192 217 235 198 181 197 196 180 184 199 163 196
pH 7.7 7.6 7.2 8.4 7.6 6.7 7.7 7.0 7.6 7.1 7.0 7.3 7.5 7.6 7.4
Eh (V) 0.39 0.41 0.39 0.38 0.39 0.43 – 0.40 0.42 0.43 0.43 0.42 0.39 0.41 0.40
DO (mg/l) 10.1 – – 9.8 9.2 – 3.9 – – – – – 10.4 – –
SiO2 (mg/l) 8.1 7.1 6.0 8.8 9.6 5.8 6.6 5.3 3.9 3.0 0.9 4.3 5.3 6.2 4.5
Ca (mg/l) 23.0 30.0 34.0 33.5 33.0 42.0 31.0 34.0 45.0 46.0 41.3 41.0 41.0 33.0 41.0
Mg (mg/l) 7.3 1.0 4.7 2.1 4.4 4.2 3.8 3.1 2.6 2.3 1.6 2.6 2.4 3.0 3.7
Na (mg/l) 5.7 13.0 3.7 9.8 2.5 3.0 2.6 2.3 1.5 0.8 0.3 1.9 2.0 1.5 1.4
K (mg/l) 0.4 0.4 0.5 0.6 0.3 0.4 0.4 0.7 0.2 0.2 0.2 0.3 0.3 0.3 0.4
HCO3 (mg/l) 106 109 113 106 110 108 104 108 141 144 130 127 122 109 127
SO4 (mg/l) 7.1 14.4 15.3 19.5 5.5 28.8 10.1 11.8 3.2 1.5 1.5 7.0 7.5 5.8 10.8
Cl (mg/l) 1.1 1.0 0.9 0.9 1.3 0.9 1.8 1.6 0.8 0.9 0.8 0.9 0.8 0.9 1.0
Al 2.6 4.5 5.4 4.6 2.7 6.1 11 3.1 6.2 9.2 6.4 6.1 5.4 1.3 16
Fe 1.7 12 23 2.8 <DL 12 23 14 11 51 41 7.0 <DL 32 41
Li 3.0 3.0 1.0 4.0 3.0 1.0 <DL 1.0 1.0 1.0 1.6 1.0 2.0 <DL 1.0
Rb 0.20 0.23 0.25 0.35 0.20 0.21 0.18 0.35 <DL <DL <DL <DL <DL <DL 0.27
G.C. Phipps et al.

Sr 920 1200 1100 1400 340 1150 450 520 1000 130 269 980 950 950 1100
Ba 87 61 64 63 220 80 150 110 130 300 160 210 230 150 130
B 74.0 140 33 105 <DL 29 <DL <DL 17 <DL <DL <DL <DL <DL <DL
V 0.30 <DL <DL 0.10 0.30 0.25 0.40 <DL <DL <DL <DL 0.90 1.00 <DL <DL
Cr <DL 0.35 0.23 0.45 0.40 0.20 0.21 1.20 <DL 0.33 0.27 0.21 0.40 0.30 0.30
Ni <DL 2.1 1.1 5.0 <DL 2.2 1.1 7.6 1.7 1.6 1.4 1.3 1.0 <DL 1.5
Co <DL <DL <DL 0.30 <DL 0.41 0.07 <DL <DL <DL <DL <DL 0.30 <DL <DL
Mn 0.4 2.4 1.6 0.6 2.3 66 22 16 2.6 4.4 2.7 11 11 1.2 2.5
Mo 6.4 5.7 6.7 4.0 1.0 10 2.7 4.7 1.1 <DL <DL 1.6 1.4 2.0 5.1
Zn 5.0 6.1 3.5 3.5 22 1400 240 680 <DL 12 14 970 1100 240 810
Cu 0.5 2.0 <DL 0.7 1.1 7.6 3.2 18 1.1 1.6 2.2 19 20 6.5 28
Pb 0.4 0.6 0.5 0.4 0.4 34 6.5 12 0.3 1.5 0.8 19 20 1.6 24
Cd <DL 4.1 <DL <DL <DL 3.2 0.97 12 <DL 0.55 <DL 4.5 5.0 1.4 3.2
As 4.0 9.0 51 12 3.0 17 15 15 2.1 <DL 1.5 8.6 8.0 7.1 8.1
Sb 1.3 1.0 1.5 0.5 1.0 25 3.3 11 0.7 0.2 0.2 6.1 5.8 4.0 18
Se 5.0 <DL <DL <DL 5.0 2.0 2.2 <DL <DL <DL <DL <DL <DL <DL 5.9
U 0.70 0.27 6.7 <DL 1.0 3.8 2.1 5.8 0.59 <DL <DL 0.49 0.50 1.6 3.1
 Groundwater geochemistry and exploration methods 339

Fig. 5. Geological section through

Price ore-body at 50+00m E (mine
coordinates) (a); and 51+50m E (b).
Groundwater chemistry from flowing
drill holes is outlined in Table 4. The
Price ore is hosted within the
Lynx–Myra–Price horizon.

Table 5. Summary statistics for groundwaters with Zn d20 µg/l associated with the Price ore-body (Price 4 and 5levels) and the ore clast breccia unit (OCB). Recode values from Table
1 are used for concentrations less than detection. Concentrations are in µg/l except where noted.

Price Ore body (n=30) Ore Clast Breccia (n=7)

Analyte Min. Median Max. Min. Median Max.
o
Temp ( C) 6.0 6.3 9.3 6.7 7.0 7.2
EC (mS/cm) 163 215 458 76 183 277
pH 6.4 7.3 8.1 7.2 7.8 8.1
Eh (V) 0.37 0.41 0.44 0.35 0.42 0.45
DO (mg/l) 3.9 9.8 11.2 5.3 9.5 18.3
SiO2 (mg/l) 3.2 5.2 9.6 2.1 3.0 4.9
Ca (mg/l) 31 40 72 15 38 53
Mg (mg/l) 2.4 3.8 12 0.45 0.92 1.3
Na (mg/l) 0.56 2.2 29 0.60 1.9 1.9
K (mg/l) 0.11 0.34 1.7 0.032 0.046 0.067
HCO3 (mg/l) 98 123 170 39 96 109
SO4 (mg/l) 4.3 13 107 5.9 15 47
Cl (mg/l) 0.59 0.88 1.8 0.38 0.51 0.61
Al 1.3 3.4 16 4.6 6.6 11
Fe 1.65 15 41 3.0 6.0 38
Li 0.13 1.0 6.0 0.13 1.0 2.0
Rb 0.003 0.20 0.80 0.003 0.003 0.003
Sr 160 965 6550 63 130 320
Ba 16 110 330 25 68 90
B 3.0 16 180 3.0 3.0 3.0
V 0.07 0.07 1.0 0.07 0.07 0.25
Cr 0.06 0.21 1.2 0.06 0.06 0.22
Ni 0.30 0.30 7.6 0.30 0.30 1.9
Co 0.01 0.01 0.41 0.01 0.01 0.60
Mn 0.60 5.3 110 1.1 1.9 11
Mo 0.01 3.5 20 0.01 4.1 6.9
Zn 20 125 1400 22 35 130
Cu 0.23 2.5 28 1.1 1.4 40
Pb 0.15 2.4 34 0.15 0.33 3.0
Cd 0.24 0.70 12 0.24 0.24 0.55
As 0.58 8.1 43 0.58 3.5 19
Sb 0.15 4.9 130 0.34 1.6 4.8
Se 1.25 1.25 12 1.25 1.25 4.2
U 0.07 1.6 5.8 0.07 0.38 0.5
Barite SI
0.32 0.074 0.67
0.81
0.05 0.28

Mean U concentrations are also significantly different for
these two environments. Uranium is slightly elevated in the
massive sulphides (Table 1), and is present in specific fault
zones as determined by geophysical logging on the property
(J. Mwenifumbo, personal communication). Median U concen-
tration in groundwaters related to Price ore is greater than the
maximum value from the OCB groundwaters.
Because the OCB unit contains little or no phyllosilicate
minerals and lacks the alteration halo present around the
volcanic-hosted primary ore, a distinct groundwater chemistry
340 G.C. Phipps et al.
results. The groundwater in contact with the OCB is character-
ized by lower concentrations of elements associated with these
lithologies as compared to water contacting the massive-
sulphide mineralization. For example K, Rb, Ba, Cd, Sb and U,
which are related to primary depositional processes and host
rock alteration, provide an effective tool in discriminating
between the Price ore-body and the OCB unit after initial
delineation of anomalous groundwaters using Zn. Elements
elevated in G-flow unit that overlies the Price deposit (i.e. Cr,
Sr, Mn and Mg) are useful in delineating proximity to the Price
massive sulphide.
SUMMARY AND CONCLUSIONS
Within the Sicker Group volcanics, rock compositions range
from basaltic to rhyolitic, and groundwater geochemistry is
effective in discriminating chemical suites of analytes associated
with the type of rock that the water has been in contact with.
For example, mafic units contribute elements such as Ni, Cr,
Co, V, Mg and Mn. Waters contacting alteration minerals
associated with mineralization are enriched in K, Rb and B.
Dissolution of sulphide minerals from the ore zone has
increased the dissolved sulphate and mobilized Zn, Cu and Pb.
The element contrasts that have developed in the ground-
water have done so in spite of the limited contact time with the
minerals. The resulting groundwaters have low dissolved solids
and near-neutral pH, and the presence of DO in most of the
groundwaters indicates that oxygen-consuming reactions have
not gone to completion.
Geochemical and statistical techniques were combined to
develop a method that can be used to further enhance existing
mineral exploration programmes of Zn-rich sulphide deposits.
Anomalies are first identified using Zn as the preferred indicator
element due to its superior mobility in the oxygenated ground-
waters typical in this setting. A threshold value of 20 µg/l Zn
was established. This concentration allows for an uncertainty of
assigning 10% of the background waters to the anomalous
population, which should represent a reasonable tolerance.
Exploration programmes in new regions may find threshold
values to differ depending on the distribution of background
and anomalous populations.
The strength of the anomaly, after initially being defined on
the basis of Zn, can then be enhanced based on a combination
of elevated concentrations of indicator and pathfinder elements
associated with either the ore deposit (Cu, Pb, Cd, Ba, U, As
and Sb), alteration minerals (Rb and B), or the minerals in
overlying stratigraphic units (Sr, Mn and Cr).
Using Zn as a definitive indicator element does not differ-
entiate between anomalous groundwaters related to massive-
sulphide mineralization and the subeconomic ore clast breccia
unit. Effective discrimination of groundwater anomalies is
possible between these two types of mineralization through the
use of elements associated with hydrothermal alteration (K, Rb
and B), primary mineralization (Ba, Cd, Sb and U) and, in this
setting, elements in the stratigraphy overlying the Price deposit
(Sr, Cr, Mg and Mn). Groundwaters associated with the
massive-sulphide mineralization have elevated concentrations
of these elements, and have higher barite saturation indices, as
compared to groundwater from the OCB unit.
As exploration programmes proceed, the chemical analyses
of water inflows into existing drifts and drill holes offer an
additional tool which can be added to the exploration pro-
gramme. This tool effectively increases the rock volume
being sampled at minimal incremental cost to the exploration
programme.
This research was supported with funding from the Industrial
Partners Project by the Geological Survey of Canada and Westmin
Resources Ltd. Lithochemical sampling was conducted by J.V.
Hamilton. Technical field assistance from G. Dirom and R. Pearson
is gratefully acknowledged along with support from the geology staff
at the Myra Falls Operation. The authors also express gratitude to the
reviewers for their constructive comments.
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