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Spring water trace element geochemistry: A tool for resource
assessment and reconnaissance mineral exploration
Marie-Eve Caron a,b,*, Stephen E. Grasby a,b, M. Cathryn Ryan a
a Department of Geoscience, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4b Geological Survey of Canada (Calgary), 3303, 33rd Street NW, Calgary, Alberta, Canada T2L 2A7
a r t i c l e i n f o
Article history:
Received 26 October 2007
Accepted 20 July 2008
Available online 19 September 2008
Editorial handling by C. Reimann
a b s t r a c t
Geochemical data from 151 spring locations within the 37,000 km2 South Nahanni River
Basin of the Mackenzie Mountains, Northwest Territories, were analysed as part of a recon-
naissance assessment of mineral potential in this large and remote region. Statistical data
analyses, graphical methods and strategic grouping of springs according to geochemistry,
pH and temperature, were used to identify regions with higher mineralization potential
quickly and efficiently. Testing of internal consistency indicates that known world class
deposits within the basin are readily detected, but by different methods. As different
deposit types have different geochemical signatures a new 3-component approach was
developed to analyze trace element data for signatures of mineralisation. Estimation of cir-
culation depth, and therefore maximum potential ore depth, further refines the assessment
of economic potential. The depth of circulation of the spring waters ranged from 4.7 km to
less than 200 m for the entire dataset. In total, 62 spring locations were identified as having
anomalous trace metal content by one or more method (approximately 40% of the dataset).
Specifically, 11 spring locations were classified as anomalous by all three methods, and 17
by at least two methods, and 34 by only one method.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
Canada is currently undergoing a process to designate
10 new national parks in the next 5 year, with the goal of
having one national park in each of the countrys 39 ecore-
gions. This represents over 300,000 km2 that will be pro-
tected in perpetuity as undeveloped natural areas
(approximately 3% of Canadas total land mass). Many of
the regions being considered for National Park designationhave little or no development, no road access, and lie in re-
mote uninhabited areas. The park creation process requires
that all long term decisions on boundaries be made with
full knowledge on potential mineral and energy resources
that would be removed from future production. This cre-
ates a challenge to assess large under-explored areas in a
short time frame, and with limited budget, for economic
mineral potential. Here the authors report a multi-method
approach developed using trace element geochemistry of
spring waters in order to assess mineral potential of a re-
gion being considered for National Park status, the South
Nahanni River Basin (SNRB). This region is already known
to host two world class mineral deposits and is thought
to have some of the highest mineral potential in Canada
(Falck and Wright, 2007). While designed to meet require-ments of Canadas National Park creation process, this
work is readily adapted to general mineral exploration.
2. Background
2.1. Overview of SNRB
The SNRB (Fig. 1) is located in the Mackenzie Mountains
east of the continental divide and encompasses two main
topographical regions: (1) the relatively flat southeastern
region which is characterized by broadly folded karstic
0883-2927/$ - see front matter 2008 Elsevier Ltd. All rights reserved.doi:10.1016/j.apgeochem.2008.07.020
* Corresponding author. Present address: Matrix Solutions Inc., 200,
150 13 Avenue SW, Calgary, Alberta, Canada T2R0V2. Fax: +1 403 263
2493.
E-mail address: [email protected] (M.-E. Caron).
Applied Geochemistry 23 (2008) 35613578
Contents lists available at ScienceDirect
Applied Geochemistry
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / a p g e o c h e m
mailto:[email protected]://www.sciencedirect.com/science/journal/08832927http://www.elsevier.com/locate/apgeochemhttp://www.elsevier.com/locate/apgeochemhttp://www.sciencedirect.com/science/journal/08832927mailto:[email protected]8/6/2019 Spring Water Trace Element Geochemistry a Tool for Resource
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uSaht
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FlatRiver
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NahanniButte
MERA I
MERA I
BSR
SouthNahanniRiverPrairieCreekMine
BrokenSkullR
iver
ApperRanges
BackboneRanges
SunbloodRange
egnaR
uobiraC
egnaRsseldae
H
egnaRlarenu
F
LandryRanges
FaciesBoundary
SELWYN
MOUNTAIN
S
SombreMountains
M
E
IE
NS
ACK
NZ
MOUNTAI
Nahanni Karst /Ram Plateau
TaigaCordillera
SouthernArctic
Taiga Shield
TaigaPlains
Canada
Extensive
Sporadic
Continuous
MacMillanPassHowardsPass
Nunavut
NWT
. AlbertaB C.
ArcticOcean
Y
ukon
(A)
(B)
(C)
Fig. 1. Location and description of the South Nahanni River Basin (SNRB). (A) Northwest Territories permafrost zones (bold font and solid lines; NRCan,
1995), ecozones (italic font and dashed lines; Wiken, 1986; CCEA, 2006), with SNRB shaded in grey, and MacMillan Pass and Howards Pass mineral deposit
locations marked with stars (both outside and north of the SNRB); (B) SNRB physiographic regions (after Mathews, 1986) with the eastern platformal
carbonate/western basinal shale facies boundary (bold, dashed line) as described by Gabrielse et al. (1965); (C) SNRB mapsheets, Sahtu/Deh Cho First
Nations groups (dashed line), waterways, infrastructure and current Nahanni National Park (NNP) boundary. Mineral and Energy Resource Assessment
(MERA) I (with two sub-areas) and II areas are marked as two dotted boxes and as theoutline of the watershed, respectively. Beaver River Structure (BSR) is
marked with a bold dashed line as proposed by Morrow and Miles (2000) in the southeastern corner of the SNRB.
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terrain, shallowly-incised topography, and inferred faults,
and (2) the mountainous northwestern region with more
complex structural geology in addition to igneous intrusions
of the Cretaceous Selwyn Plutonic Suite and glacially-
eroded terrain. The Ram Plateau, which is dominated by
karst features, borders the northeastern corner of the cur-
rent National Park (Brook and Ford, 1980; UNEP-WCMC,
2002).
The geology of the SNRB includes five major compo-
nents (Gordey and Anderson, 1993): Late Precambrian to
Middle Devonian carbonate platform-shale basin assem-
blage, Devono-Mississippian turbidite basin assemblage,
Mississippian to Triassic clastic shelf assemblage, regional
Jurassic-Cretaceous deformation, and granitic intrusions
of the Mid-Cretaceous Selwyn Plutonic Suite crosscutting
the regional structure. Not included in Gordey and Ander-
son (1993) is the modern shortening of the Mackenzie
Mountains at an average of 4 mm/a (Gendzwill, 1994;
Hyndman et al., 2005). There is high heat flow in the north-
ern Canadian Cordillera, estimated to be 105 22 mW/m2
(Lewis et al., 2003), with an estimated geothermal gradient
of 2331 C/km (Hyndman et al., 2005).
The authors combined the main geological units of
Okulitch (2005), into lithological groupings relevant to
groundwater geochemistry in the SNRB (Fig. 2), defined
as: (1) carbonates (limestone and dolostone, sometimes
containing bedded evaporites such as gypsum/anhydrite,
and calcareous shales, e.g., Bear Rock, Tetso, Mount Cap,
Saline River, Little Dal Group and Redstone River forma-
tions), (2) siliceous shales (often sulphide-containing, e.g.,
Besa River Formation of the Earn Group), (3) sandstones
(often containing coal, which is potentially sulphidic, e.g.,
an unnamed Eocene clastic unit, and the Wapiti, Summit
Creek, Little Bear and Mattson formations), and (4) plu-
tonic rocks (the Selwyn Plutonic Suite). A clastics division
is used to lump siltstones, mudstones and stratified miscel-
laneous units (e.g., Vampire Formation; Okulitch, 2005).
The proposal for incorporation of the SNRB into a na-
tional park would be an expansion of the existing Nahanni
National Park Reserve that was first designated in 1976.
This existing park became a World Heritage Site in 1978
when at the same time three areas were chosen for possi-
ble future expansion: The Ragged Range, the Tlogotsho Pla-
teau, and the Nahanni Karst (Fig. 1). In consequence, a
Mineral and Energy Resource Assessment (MERA I) was
conducted in those areas ( Jefferson and Spirito, 2003),
including examination of spring waters (Hamilton et al.,
1988, 1990; Gulley, 1993). The more recent proposal to in-
clude the entire watershed of the South Nahanni River in
the National Park Reserve has triggered a second, larger
MERA study (MERA II). This spring study forms one compo-
nent of the MERA II study, which also includes airborne
geophysics, stream sediment sampling, and hard-rock
geology exploration. Complete results of this MERA II study
can be found in Falck and Wright (2007) and spring water
geochemistry in Caron (2007).
2.2. Known mineral occurrences of the SNRB
Although under-explored, the SNRB is thought to have
some of the highest undiscovered mineral potential in
Canada, given known major deposits within the basin
and significant deposits in adjacent areas hosted in geo-
logic units which extend into the study area.
There are currently two known world class deposits in
the SNRB: (1) Tungsten (also known as Cantung Mine)
and, (2) Prairie Creek (Fig. 1C). Cantung Mine is a base me-
tal WCu skarn deposit, currently holding at least 12% of
the worlds W reserves (ITIA, 2005), with the total deposit
size still undefined. Magmatism in the SNRB region is gen-
erally associated with W mineralization and/or AuCuSb
BiPbZn metal occurrences (Rasmussen et al., 2006),
however, the potential for other similar deposits to Can-
tung has not been assessed. Prairie Creek Mine is one of
Canadas largest PbZn deposits at 11.8 million tonnes,
with 12.5% Zn, 10.1% Pb, 161 g/t Ag and 0.4% Cu (GNWT,
2005). It is the highest grade Mississippi Valley-type de-
posit (Pb + Zn as wt%), and is in the top six for total geolog-
ical resources (production + remaining) in Canada
(Hannigan, 2006), based on a limited deposit definition.
Placer Au potential also exists in the Ragged Ranges and
northern Liard Range-southern Ram Plateau area (Hamil-
ton et al., 1988; INAC, 2001).
Important sedimentary-exhalative (SEDEX) deposits oc-
cur adjacent to the SNRB near the Yukon/NWT border ( Yu-
kon Geological Survey, 1996), with host rocks continuing
into the SNRB (Heon, 2003), indicating the potential for
similar deposits in the SNRB region.
2.3. Geochemical exploration
Previous hydro-geochemical studies of spring waters
have been largely designed to predict environmental im-
pacts of mines (Plumlee and Logsdon, 1999), rather than
for exploration purposes. The US Geological Survey has
conducted extensive surveys of stream and spring samples
in watersheds close to mined regions in order to improve
the understanding of environmental impacts (e.g., Miller,
2002; Wanty et al., 2006). Previous studies have found sig-
nificant geochemical trends, such as the Mississippi Valley-
type deposits that were associated with anomalous PbZn
concentrations (>20lg L1) in 143 spring samples in a re-
gion of Arkansas, USA, approximately 100 km2 in size
(Steele and Dilday, 1985). There are many more examples
in the literature of environmentally-oriented, hydro-geo-
chemical studies from around the world (e.g. Leybourne
et al., 1998; Eppinger et al., 2002; Verplanck et al., 2004;
Sidenko and Sherriff, 2005).
Hydro-geochemical prospecting is not a new idea
broad discussions can be found in Runnells (1984), and
anomaly-determination techniques have been described
in detail in Giblin (2001). Mineral deposit models and their
related geochemistry are well-established, such as Cox and
Singer (1986) and Seal and Foley (2002). More recently, hy-
dro-geochemistry has been incorporated into these (Plum-
lee et al., 1994; du Bray, 1995; Plumlee, 1999; Wanty et al.,
2006). Primary factors affecting deposit drainage-water
chemistry have been shown to be: the extent of exposure
of the deposit, the grade of mineralization, amount of car-
bonate rocks (which buffers pH and reduces mineral solu-
bility), and proportion of Fe-sulphides in the ore (Kelley
and Taylor, 1997).
M.-E. Caron et al. / Applied Geochemistry 23 (2008) 35613578 3563
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Most previous hydro-geochemical groundwater pros-
pecting studies have been restricted to areas with large
pre-existing well networks, such as in Australia (Giblin,
2001; de Caritat and Kirste, 2005). One-hundred shallow
wells ( 0.9%) cluster in three groups:
sandstone-related, pluton-related and fault related.
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USA, were linked to Mississippi Valley-type deposits via
elevated Sr concentrations (Deering et al., 1983). With
the absence of wells in the present large remote study area
springs are relied on as natural discharge of groundwater.
Previous work in the southern Canadian Cordillera (Grasby
and Hutcheon, 2001) has shown that deep circulation of
meteoric water, and discharge of groundwater as discrete
springs, is often controlled by geologic features similar to
those that focused movement and deposition of hydrother-
mal ore deposits, making it likely that modern day spring
circulation systems may intersect hidden ore deposits.
Previous spring geochemistry research in the MERA I re-
port ( Jefferson and Spirito, 2003) focused on statistical
means of classifying springs based on geochemical proper-
ties. While this approach is successful at sorting springs
into groups of similar characteristics, this may or may
not imply similar hydro-geochemical history of the spring
water. From these classifications high metal content
springs were identified as a group. However, as this classi-
fication was based on major ions as well as trace elements,
there was no clear assessment of the variability of total or
individual trace elements in waters of the study area.
While springs with high or anomalous metal concentra-
tions are discussed in the study, the terms are somewhat
poorly defined. To overcome these deficiencies a new geo-
chemical exploration approach was developed that can
quickly identify mineralized zones in a large area given a
limited budget and field season. To ensure consistency of
results through both MERA I and II, data reported by Ham-
ilton (1990) and Jefferson and Spirito (2003) were also
reanalyzed using the new methods.
3. Methods
3.1. Field methods
Previously known springs were located based on earlier
reports (Brandon, 1965; Souther and Halstead, 1973;
Crandall and Sadlier-Brown, 1976; Hamilton et al., 1988;
Hamilton, 1990; Jefferson and Spirito, 2003). A total of 16
spring locations from the MERA I report were resampled.
New spring locations were found by sighting from a heli-
copter in the summer months in August 2004 and June/
July of 2005. A bare patch of ground within a vegetated
area, a spot of colouring (usually a red or white zone of pre-
cipitate, or a bright green patch of microbial mats), and
creeks flowing out of bedrock or rock debris, were someof the visual clues used. Since both field seasons took place
in the summer months, seasonal variations such as rain or
snowmelt dilution of spring water, typically dominant in
the spring, were avoided.
At each spring, a GPS location was obtained, and Eh, pH,
electrical conductivity, dissolved O2 and temperature were
measured as close to the outlet as possible. Data from
springs sampled during the MERA I study (Hamilton, 1990;
Jefferson and Spirito, 2003) were included, where possible,
in the analyses in order to provide consistent anomaly
detectionacrossthe region. MERA I datalack silicameasure-
ments suitable for aqueous geothermometry, so circulation
depths for those springs were not assessed. A total of 16
spring locations from the MERA I study were resampled to
ensure consistency between data sets. Accounting for field
duplicates andresamplingof selectedsites,a total of 151un-
ique spring locations were sampled in MERA I and II (with
approximately half in each study). One spring location
may have morethanone closely spacedoutletthatwas sam-
pled(within100 m radius) that typicallyshow similar water
geochemistry. In total, over 200water samples from the151
spring locations were analysed as part of this study. Anaver-
age concentration of each element was calculated for loca-
tions with duplicate or triplicate samples.
For this work, a typical, complete water sample was
passed through a 0.45 lm filter and separated into several
aliquots for analysis: cations and trace elements (field
acidified to a pH < 2 with ultra pure HNO3 for preserva-
tion), anions, alkalinity, silica (10 mL; with dilution factor
of six to inhibit precipitation), and d18O and d2H. The filter
apparatus was rinsed with distilled water once, and with
filtered sample water three times, prior to sampling at
each spring. New sample bottles (HDPE) were rinsed with
filtered sample water before filling. The samples were kept
in coolers and fridges until laboratory analysis in the GSC
Laboratories in Ottawa for the major ions and trace ele-
ments, and in Quebec City for the isotopes, within 4
months of collection.
3.2. Laboratory methods
Due to constraints of remote field work, alkalinity was
not measured until immediate return to the laboratory
using an Orion 960 Autotitrator with H2SO4(aq) and ROSS
pH electrode. Good charge balances, and arguments by
Drever (1997) that carbonate alkalinity is conservative
provide assurance that measured values are accurate. An-
ions were measured using Ion Chromatography and cat-
ions and trace elements were measured using Inductively
Coupled Plasma emission spectrometry/mass spectrome-
try in the Ottawa GSC Laboratory. Based on duplicates as
well as field and laboratory blanks, analytical error in con-
centration measurements was estimated to be 3% for major
ions and 7% for trace elements. Ninety percent of these
new samples have a charge balance
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interaction, a broad range of geochemical signatures
indicating water flow through mineral deposits could de-
velop. To address this, a multi-pronged approach was
developed to detect mineralized zones through indicator
or anomalous springs in the South Nahanni River basin.
The assumption is that no single geochemical method
can detect all potential deposit types. Instead three dif-
ferent methods of detection were used (total trace ele-
ments, individual trace elements, and a Ficklin
Diagram). These methods are described below. Detection
by any one method is considered sufficient condition to
classify a spring as anomalous. Detection by more than
one method provides additional support but does not
imply a stronger likelihood of a deposit being present
in the groundwaters flowpath.
There are many published references which describe
how to define natural background concentrations and
threshold values. For example, Reimann and Garrett
(2005) acknowledge that background values can vary even
between and within regions, depending on location and
scale, and that an anomaly is defined as a deviation from
the norm. In this paper, the concentrations assigned to be
elevated or anomalous in nature are still within the natural
background range of the SNRB, since very little human
development has occurred in this watershed. Rather, this
paper attempts to compare the observed elevated values
(above a certain arbitrary threshold) with other docu-
mented concentrations related to known mineral deposits.
Since there was a sampling bias towards springs that could
be seen visually from a helicopter, the coverage of the
SNRB was irregular and incomplete, and no consistent nor-
mally-distributed data analysis could be performed. For
these reasons, a preliminary reconnaissance methodology
has been developed.
The approach was tested by assessing the two known
major deposits in the region, the Tungsten and Prairie
Creek mines, as well as other deposits from around the
world. MERA I and II data were combined to determine
background levels of total and individual trace elements
in the South Nahanni River basin, MERA I samples were
also reanalyzed to provide a consistent definition of anom-
alous spring waters throughout the South Nahanni area. A
summary of the number of springs identified with elevated
total or individual trace elements (i.e. anomalous) is pro-
vided in Table 1. For the purpose of this study, trace ele-
ments are defined as anything but major ions and cations
(Na, K, Ca, Mg, Cl, HCO3
and SO4
). Total dissolved solids
(TDS) are defined as the sum of the concentrations of the
major ions.
3.4. Total trace elements
Total trace element mass concentrations (mg/L) for
each sample were normalized after Giblin (2001) by divid-
ing them by TDS, and were labelled as elevated in trace ele-
ments if they were above the 75th percentile of the SNRB:
Sum of Trace Elements in mg=L=Sum of TDS in mg=L
%Trace Elements
1
The 75th percentile for spring samples from the SNRB was
calculated to be total trace elements = 0.9% of TDS. The
springs elevated in trace elements were then plotted on a
Piper Diagram in meq/L where geochemical groupings
were identified and linked to major ions, pH, temperature
and the bedrock geology map. This method can detect a
variety of potential deposit types, because it lumps all
the trace elements into one parameter. This method iden-
tified 37 out of 151 spring locations as having anomalous
total trace elements (24.5% of the dataset).
3.5. Individual trace elements
Individual trace element concentrations for the entire
data set were analysed and the 93rd percentile calculated.
This was used as a cut off to define concentrations of indi-
vidual trace elements >93rd percentile as anomalous rela-
tive to the background values of the South Nahanni River
basin. For elements that are only detected in a few springs
(e.g., Ag in eight springs), all occurrences of detection are
considered anomalous for that element. On the other hand,
some elements are very common (e.g., Cu or Zn in almost
all springs) and therefore need a higher cut-off to be de-
fined as anomalous. Non-detectable concentrations were
estimated as half of the detection limit for the purposes
of this calculation.
A large variety of combinations and permutations of
anomalous elements in the environment can indicate dif-
ferent mineral deposits. For example, a possible sedimen-
tary exhalative deposit is indicated by Ag seen in
combination with additional trace elements (e.g., Cu, Au,
Zn) in the rock material (Cox and Singer, 1986). As another
example, sedimentary Mn deposits leave a geochemical
signature of Ba, Mn, P and Pb in the rock material (du Bray,
1995). These anomalies found in rocks are likely to be dif-
ferent in water, depending on the mineral solubility, and
pH, Eh and salinity of the solution. Geochemical signatures
from deposit models by Cox and Singer (1986) have, on
average, nine anomalous elements, although some have
as few as one or as many as 19. For the purposes of this
study, there were 26 spring locations with three or more
individual trace elements elevated above the 93rd percen-
tile (equivalent to 17.2% of the dataset).
3.6. Ficklin Diagram
The Ficklin Diagram was designed specifically to predict
environmental impacts of mining, i.e., the buffering capac-
ity of an area and its potential released trace element con-
centrations using six indicator metals, for different deposit
types for both natural and man-made acid drainage (Plum-
lee, 1999). This graphing method was primarily designed
for waters flowing near or through sulphide deposits. The
graphing method involves plotting the pH of the water
sample on thex-axis, and the sum of six key metal concen-
trations (Zn, Pb, Cu, Co, Ni and Cd) on they-axis. The higher
the pH of the water, the greater the buffering of the sys-
tem; and the higher the sum of the six key metal concen-
trations, the higher the base-metal content of the deposit
(Plumlee, 1999). Water samples from similar deposit types
tend to plot in clusters, with varying degrees of buffering
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Table 1
Summary of three methods for determining anomalousness
Spring name
(informal)
Total TE as %
of TDS
Ficklin
Diagram field
Geo-chemical
group
Estimated circulation
depth (km)
# of
elevated TE
Elevated trace elements (TE)
Prairie Creek Mine Water 2.74 H 1
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Table 1 (continued)
Spring name
(informal)
Total TE as % of
TDS
Ficklin Diagram
field
Geo-chemical
group
Estimated circulation depth
(km)
# of elevated
TE
Elevated trace elements
(TE)
Tabletop 0.63 2.3 1 Sr
Red Steel 0.63
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capacity and metal concentrations (Plumlee, 1999). This
method is largely restricted to identifying sulphide related
mineral deposits and has limited use for other deposit
types.
In the study this approach was inverted, by using the
natural environmental conditions to predict the deposit
types that are likely influencing the spring water chemistry
(Fig. 6). Spring waters plotted on the Ficklin Diagram can
be assessed as to whether or not they fall into fields for
various ore deposit types that have been defined by the
trace element geochemistry of mine waters associated
with known mineral deposits. Overall, 39 spring locations
from the South Nahanni Watershed fell within one of the
Ficklin Diagrams ore deposit fields (equivalent to 25.8%
of the dataset).
3.7. Geothermometry
Based on outlet temperature samples were classified as
cold below 12 C, warm between 12 C and 40 C, and
hot above 40 C. To obtain estimates of maximum tem-
perature along the circulation path aqueous geothermom-
eters were applied. Silica geothermometry (chalcedony)
was deemed most appropriate for the SNRB springs, fol-
lowing Grasby and Hutcheon (2001). Since low tempera-
ture Na/K ratios are controlled more by non-equilibrium
mineral dissolution (i.e., kinetic factors and residence time)
than by chemical equilibrium, they may cause erroneous
results (Mutlu and Gulec, 1998) and are slow to equilibrate
in low temperature settings. Generally, high-temperature
reservoirs are usually studied with the quartz geother-
mometer, and low-temperature (0.9%), while in contrast none of
Table 1 (continued)
Spring name
(informal)
Total TE as % of
TDS
Ficklin
Diagram field
Geo-chemical
group
Estimated circulation
depth (km)
# of elevated
TE
Elevated trace
elements (TE)
Cordes Vertes 0.11 n/a 0 n/a
8666 0.10 IJK 0 n/a
North Cantung (8644,
Zenchuck Creek)
0.10 1.3 0 n/a
Cascade 0.10
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the Prairie Creek deposit related waters are above (Table
3). In other words the total trace element method would
detect Tungsten, but not Prairie Creek, as anomalous.
On the Ficklin Diagram, the Prairie Creek deposit plot-
ted in the correct ore deposit field (Group H: pyrite- and
base-metal-rich polymetallic replacements and veins in
carbonate-rich sediments; Fig. 6) in two out of three near-
by water samples. In contrast, the Tungsten deposit did not
plot in any deposit field, consistent with the fact that it is
not a sulphide hosted system.
In summary, the two major or deposits in the study
area, Prairie Creek and Tungsten, were each detected by a
different combination of two out of three of the methods
used, but not by all three. This test demonstrates well
the need to utilize a multi-pronged approach. Any single
method of geochemical exploration based on water chem-
istry may miss a world class mineral deposit.
4. Results
The locations of 151 springs within the SNRB were de-fined by the authors and previous workers. Discharge var-
ies from small outlets flowing less than 0.001 m3/s, to large
discharge estimated at several m3/s. Springs within the ba-
sin show a broad range of temperature from 0 C to 64 C.
All hot springs (>40 C), and most of the warm springs (12
40 C), are found in the northwestern side of the SNRB,
while cold springs ( 7). Warm/hot springs are
Table 3
Testing the multi-method approach using the two known deposits of the SNRB
Related deposit Sample Total trace
elements(%)
Individual trace
elements
Ficklin Diagram
group
Geo-chemical
group
Samples near or from
Cantung
(a.k.a. Tungsten) Mine
Tungsten Mine water 1.00 Ag n/a 3
Stinky Drift 0.16 Tl n/a n/a
West Cantung 1.42 Cs, Li,V, B, Ga n/a 3
Samples near or from
Prairie Creek mine
Prairie Creek Mine
Water
0.81 Cu,Zn, Pb, Cd, Sb, Tl, Se H n/a
Prairie Creek 0.14 Sb, NO2 IJK n/a
Harrison Creek 0.08 Pb n/a n/a
Galena 0.13 Pb, U, Tl, Se J n/a
Galena (lab duplicate) 0.13 U,Tl J n/a
Note: Total trace elements are normalized as a percent of total dissolved solid for each sample.
M.-E. Caron et al. / Applied Geochemistry 23 (2008) 35613578 3571
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all near-neutral or basic and not dividableby pH excluding
Stinky Drift sampled directly from a mine shaft. Overall, this
gives three major groups of springs: (1) cold and basic, (2)
cold and acidic and (3) warm/hot and basic. These tempera-
ture and pHgroups canbe related to the bedrock from which
they discharge. Most cold and acidic springs discharge from
siliceous shales (15) while the rest are from a mixture of car-
bonates (12), plutons (6) and clastics (4). Acid springs dis-
charging from units defined as carbonates are related to
pyritic shales inter-bedded with the carbonates. Cold and
basic springs mostly dischargefromcarbonates (65)or from
calcareous shales (36). Springs discharging from calcareous
shale showsimilar characteristics to those discharging from
carbonates such as limestone and dolostone (Caron, 2007)
and are distinct from springs discharging from siliceous
shales. Warm/hot, basic springs discharge dominantly from
carbonates (33) while the others are from a mixture of cal-
careous shale (14), clastics (9) and plutons (8).
4.3. Predicting mineralization using trace element
geochemistry
4.3.1. Total trace elements
In this study, springs indicating the greatest economic
potential have total trace element concentrations above
the 75th percentile as a percentage of total dissolved solids
(>0.9%). Only the coldest and hottest waters of the SNRB
are defined as elevated in total trace elements relative to
TDS, while springs with moderate temperatures between
12 C and 40 C have total trace elements below the 75th
percentile (0.9% of TDS). For hot springs, only Na-rich
waters are elevated in total trace elements, whereas Ca-
rich hot springs are not. Hot, basic, Na-rich waters elevated
in total trace elements are associated with large faults near
plutons. Hot, basic, low metal-content, Ca-rich hot springs
are also associated with large faults but typically are lo-
cated far from plutons. Anomalous total trace elements oc-
cur in both acidic and basic waters, suggesting that pH is
not a dominant influence on detection of anomalies with
this method.
Springs with TDS-normalized total trace elements
greater than 0.9% cluster into three distinct groups on a pi-
per diagram (Fig. 4). Considering temperature and pH, the
groups can be defined as follows: Group 1 SO4- and
HCO3-rich, basic (pH$8), and cold (
8/6/2019 Spring Water Trace Element Geochemistry a Tool for Resource
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0.01
0.1
1
10
100
1000
10000
100000
1000000
concen
tra
tion
(g
L-1)
Fe
Al
Mn
Ni
Cu
Pb
Cd
Co
Cr
Cs
Mo
As
Li
Rb
Sr
Ba
UV BSb
Tl
Ga
Se
Br
Ag
Be
Sc
Ti
Bi
In
NO2
Zn
Trace element for springs with detectable concentrations
min
max97th93rd75thmedian
25th
Fig. 5. Trace element statistics for SNRB springs: minimum, 25th, 50th, 75th, 93rd and 97th percentiles, and maximum concentrations for all MERA I and IIspring locations.
Fig. 4. Piper plot of SNRB springs major ions based on meq/L. Springs with elevatedTDS-normalized trace elements (T.E. > 0.9%) have filled symbols and fall
into three distinct groups: (1) Cold, basic and HCO3SO4-rich; (2) Cold, acidic, and SO4-rich; and (3) Hot, basic and Na-rich. There are no anomalous warm
springs (except for Tungsten mine water drainage), and no anomalous acidic hot springs (n/a). Dotted rectangles in the lower left-hand triangle highlight
the linear trend of warm springs from Ca to Na richness, and the two clusters of hot springs: Ca-rich on the left and Na-rich on the right. These symbols are
used in other figures throughout this paper.
M.-E. Caron et al. / Applied Geochemistry 23 (2008) 35613578 3573
8/6/2019 Spring Water Trace Element Geochemistry a Tool for Resource
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with an average of 1.36, summarized in Table 1. Some
spring locations have few elevated trace elements (e.g.
Ag and Tl in Tungsten Mine Water, or Pb in Flat Fruit)
and some have multiple ones (e.g. Cu, Zn, Pb, Cd, Sb, Tl,
Se and Ag in Prairie Creek Mine Shaft, or Al, Mn, Ni, Cu,
Zn Cd, Co and Ag in Bougere). Twenty-six spring locations
were found to have more than three anomalous individual
trace elements (equivalent to 17.2% of the dataset).
4.3.3. Ficklin Diagram
There are 39 spring locations that fall in or near delin-
eated ore deposit fields as outlined in the Ficklin Diagram
ofPlumlee et al. (1994), of which 25 have TDS-normalized
total trace elements above the 75th percentile (0.9%) and
36 have elevated individual trace elements (Fig. 6; Table
1). On the other hand, 27 samples with total trace elements
above the 75th percentile do not fall in or near any delin-
eated fields. Samples that plot on the right-hand side of
the diagram have high acid-buffering capacity, while sam-
ples plotting on the left-hand side have low acid buffering
capacity (Plumlee et al., 1994). The sum of the concentra-
tions of 6 trace elements (Zn, Pb, Cu, Co, Ni and Cd; on
the y-axis) are proportional to the size or distribution of
a given sulphide deposit. Based on empirical work ofPlum-
lee et al. (1994) fields defining where waters characteristic
of different mineral assemblages associated with known
ore deposit types are also shown. Above a sum of 0.5 on
the y-axis, springs with d34SSO4 values consistent with oxi-
dation of sulphide deposits of the area (Caron, 2007) all fall
in one of the delineated sulphide ore fields ofPlumlee et al.
(1994): J, K, G, F, E and H (Fig. 6). As these fields represent
the geochemistry of waters flowing through known depos-
its, they are used as indicators of potential deposit types in
the SNRB. For the two known world class deposits in the
SNRB, Prairie Creek mine water from the eastern side of
the SNRB plots in the correct deposit type (Group H Pyr-
ite- and base-metal-rich, poly-metallic replacements and
veins in carbonate-rich sediments), while Tungsten Mine
water (a non-sulphide deposit) does not fall in any delin-
eated field as would be expected given the Ficklin Diagram
is designed only for sulphide deposits.
4.4. Relative accessibility of mineralized zones using
geothermometry
As is typical of mountains devoid of active volcanic
activity, the main heat source of the region is the back-
ground geothermal gradient (Lewis et al., 2003). Based on
the results of the aqueous geothermometers employed,
and an estimated geothermal gradient of 23 C/km (Hynd-
man et al., 2005), the average depth of circulation of the
analyzed springs in the SNRB is 2.1 km, the deepest being
4.7 km for the Brimstone Spring and the shallowest being
less than 0.2 km at Cotton (standard deviation = 1.2 km,
n = 32; Table 1). Corresponding temperatures at depth
range from 5.5 C to 108 C, with an average of 48 C. These
are considered minimum estimates of the systems highest
temperatures since dilution and re-equilibration of waters
would lower the calculated temperatures (Grasby and Hut-
cheon, 2001) and advective heat flow along faults would
lower the geothermal gradient (Forster and Smith, 1988).
The estimates of depth of circulation obtained via Si-geo-
thermometry are consistent with other work done on some
of the previously studied springs (Brandon, 1965; Hamil-
EG
H
JI
K
F
Prairie CreekMine Water
0.001
0.01
0.1
1
10
100
2 3 4 5 6 7 8 9 10
pH
Zn
+Pb+Cu
+Co
+Ni+Cd(mg
L-1)
TungstenMine Water
Group 1: Cold & Basic Trace Elements < 0.9 %
Group 2: Cold & Acidic also shows sulphide oxidation
Group 3: Hot & Basic Total Tungsten mine water
Fig. 6. Ficklin Diagram showing spring samples grouped by total trace elements >0.9% relative to TDS (Groups 13). Other spring samples are shown as
small black dots and have total trace elements
8/6/2019 Spring Water Trace Element Geochemistry a Tool for Resource
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ton, 1990; Gulley, 1993). All other springs, with low tem-
peratures and low silica concentrations, are assumed to
circulate less than 200 m and were not analyzed using sil-
ica geothermometry due to the potential of errors.
5. Discussion
5.1. Geologic controls on spring geochemistry
Out of a total 151 spring locations examined here, five
samples elevated in trace elements were hot, basic, Na-rich
and discharging near plutons (Group 3 from the piper plot
ofFig. 4), 16 were cold, basic, SO4HCO3-rich and discharg-
ing from mostly calcareous shale and carbonate rock
(Group 1), and 20 were found to be cold, acidic, SO4-rich
and discharging mostly from siliceous shale (Group 2).
The Na-rich hot springs have significantly higher values
of TDS-normalized total trace elements (average is
1.13 0.16%) than Ca-rich ones (0.31 0.15%). Sodium-rich
hot springs tend to originate out of plutonic rock, near a
contact with plutonic rock, or from the Flat River Valley,
which is bordered on each side by plutons and underlain
by them as well. These same Na-rich hot springs were de-
scribed as having a granitic influence, as opposed to the
others as having a sedimentary origin (Crandall and Sadli-
er-Brown, 1976).
The springs defined as anomalous based on the trace
element data were compared with the geology map simpli-
fied from Okulitch (2005), which allowed for a delineation
of three main clusters (Fig. 2): (1) sandstone-related anom-
alous springs (Mattson Formation) which can be explained
by the pyritic nature of the sandstone and its coal deposits
south of the basin (Stott, 1982); (2) anomalous springs
near major faults and fractures, mostly on the western side
of the basin near the Flat River Valley and Broken Skull Riv-
er, which may be explained by the observed presence of
mineralization in these types of structures in other places
in the basin (e.g., Morrow and Miles, 2000; Prairie Creek
mine); and (3) pluton-related anomalous springs (Selwyn
Plutonic Suite). The pluton-related anomalous springs are
either discharging directly from the plutons themselves,
or within a radius of 5 km around the contact with the
country rock. This is consistent with metamorphic contact
aureoles documented by Blusson (1968) where these
anomalous springs are found. The Tungsten Mine is located
within one of these halos of deformation (Blusson, 1968).
Overall, springs elevated in trace elements tended to dis-
1)gaseous and deep
+ shallow mixture
2) cold, shallow& acidic
(discharging from pluton-Na-rich)
(discharging from carbonate)
4)warm & evaporite
dissolution( e.g.:CaSO4
8) cold and acidic &high T.E.
(discharging fromshale)
6)hot andbasic
3) cold and basic
without evaporitedissolution
Pluton Shale Carbonatealteration
halo
mantlegases?
dissolved evaporite evaporites
& low T.E., Ca-rich
5) hot and basic
& high T.E., Na-rich
7) cold and basic & low T.E
not to scale
~5km
Fig. 7. Conceptual model of water flow paths for the variety of spring types in the SNRB. (1) Deep, gaseous water mixing with shallow meteoric water; (2)
shallow, cold and acidic water discharging from tops of plutons via fractures or talus; (3) shallow, cold and without signs of evaporitedissolution, due to the
lack of shallow evaporites in the region (although they may have been present in the past and now are dissolved away); (4) warm with signs of evaporite
dissolution; (5) hot, basic, Na-rich and high in total trace elements discharging from deformation halos around plutons; (6) hot, basic, Ca-rich and low in
total trace elements discharging from faults far from plutons; (7) cold, basic, low in total trace element, HCO 3-rich water discharging from carbonate; and
(8) cold, acidic, high in total trace element, SO 4-rich water discharging from sulphide-containing shale. Diagram is not to scale. Depth of gaseous spring
circulation is approximately 5 km and evaporites are present at depths below approximately 300 m. Shape of plutons was modified from Hamilton et al.(1990). More types of springs exist that can fit on this diagram.
M.-E. Caron et al. / Applied Geochemistry 23 (2008) 35613578 3575
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charge near plutons (western side of SNRB), faults and frac-
tures (throughout), and from rocks that are in contact with
the Mattson Formation (eastern side of SNRB).
Given the main source of heat of springs is the back-
ground geothermal heat flow (Lewis et al., 2003), it can
be inferred that the cold and acidic springs circulate at
shallower levels compared to the warm or hot springs.
The lack of acidic warm or hot springs could be due to
the fact that deeper-circulating springs are more likely to
flow through carbonate rocks and therefore be buffered,
similar to the deep, high pH springs discharging from plu-
tons in Europe (Michard, 1990). Also, the presence of plu-
tons on the western side of the basin adds another
source of buffering because weathering of feldspars to
clays is an acid-consuming reaction (Appello and Postma,
1999). Feldspar weathering and ion-exchange reactions
also generate the Na-rich springs associated with plutons.
Similar factors controlling spring geochemistry have been
observed in the southern Canadian Cordillera (Grasby
et al., 2000).
Fig. 7 illustrates a conceptual model of spring systems
within the SNRB to explain how variations in geology influ-
ence depth of circulation and aqueous geochemistry ob-
served in springs of the SNRB. This is summarise as: (1)
deep springs flowing near plutons that are sometimes gas-
eous and mixed with shallower water, (2) shallower
springs discharging from plutons which are relatively fresh
and Na-rich, (3) shallower springs discharging away from
plutons with relatively low TDS and no signs of evaporate
dissolution (although evaporites may have once been pres-
ent at these shallow depths, they are now all dissolved
out), (4) moderately deep and warm springs with elevated
TDS that are flowing through evaporite layers, (5) deep,
Na-rich hot springs discharging near plutons with elevated
trace elements, (6) deep, Ca-rich hot springs flowing far
from plutons that are not elevated in trace elements, (7)
shallow springs flowing through carbonates that are not
elevated in trace elements, and (8) shallow springs flowing
through siliceous shales that are elevated in trace
elements.
5.2. Prioritizing future mineral exploration
A summary of the trace element analysis is listed in Ta-
ble 1 for each spring along with its estimated circulation
depth, which can be used to prioritize more detailed explo-
ration work. The springs are listed first by order of geo-
chemical Group (1, 2 or 3), then by the number of
anomalous trace elements, and lastly by TDS-normalized
total trace elements. The priority for future exploration
should focus on a combination of the shallowest, most buf-
fering and most mineralized springs (such as Group 1, i.e.,
cold and basic springs with above average total trace ele-
ments), because cold and basic springs which are elevated
in trace elements are likely detecting a more accessible
mineralized zone with a higher buffering potential (which
can help mitigate potential environmental impacts). To re-
fine the exploration phase, one can use the individually
elevated trace elements or Ficklin Diagram groupings to
help predict the type of mineralization present.
6. Conclusions
This study demonstrates that regional sampling of
spring discharge and analyses of trace element data can
provide a rapid and relatively low cost reconnaissance
exploration tool. A 3-component approach was employed,
including statistical analyses and graphing methods, to
identify waters likely associated with mineralized zonesquickly and efficiently in a largely under-explored area.
The methods include summing trace element concentra-
tions as a percentage of total dissolved solids, identifying
individual anomalously-high trace elements, and using a
Ficklin Diagram (Plumlee et al., 1994). Results identify
62 springs from the SNRB that are deemed to have anom-
alous trace element characteristics as detected by one or
more of the three methods used here (37 spring locations
with elevated concentrations of TDS-normalized total
trace elements, 26 with three or more anomalously high
individual trace elements, and 50 samples (or 39 loca-
tions) that plot in fields characteristic of known mineral
deposits on a Ficklin Diagram). Specifically, 11 springslocations were classified as anomalous by all three meth-
ods, 17 by at least two methods and 34 by only one
method. The assessment of spring water data from the
previous MERA I study ( Jefferson and Spirito 2003) re-
sulted in reclassification of 12 springs from the MERA I
study as anomalous.
The two currently known world-class deposits of the
South Nahanni River Basin (Tungsten and Prairie Creek;
Fig. 1C) were successfully detected by two of three meth-
ods, but not by the same combination, demonstrating the
advantage of using a multi-method approach. Individual
geochemical methods may not have detected world class
deposits. Overall, the large number of spring samples usedin the analyses allows for a large, regional, watershed-
based understanding of the South Nahanni River Basin geo-
chemistry and its related mineral potential. No single ap-
proach is suitable, however, for detecting anomalous
metal concentrations related to the diverse suite of deposit
types found in the SNRB. A multi-method approach can
identify mineralized zones quickly and efficiently in a
large, under-explored area, consistent with trends ob-
served in the bedrock geology and other exploration
methods.
The methods developed in this work are adaptable for a
variety of geologic terrains, which can be used for future
MERA (or similar) assessments, in addition to regional geo-chemical prospecting and environmental baseline studies.
For remote regions without developed well networks
springs are an effective tool for regional geochemical stud-
ies because they are relatively easy and inexpensive to sam-
ple, and are natural groundwater outcrops which retain
characteristics of the rocks they flow through. Springs ele-
vated in total or individual trace elements, normalized to
TDS and above background concentrations, can be used as
indicators to the overall elevated mineral potential of the
region, and ideally guide future field work and/or decision
making. The Ficklin Diagram, originally developed for pre-
dicting environmental impacts, was readily adapted for
the purpose of mineral exploration.
3576 M.-E. Caron et al. / Applied Geochemistry 23 (2008) 35613578
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It is recommended that decision makers of future na-
tional park boundaries consider the economic potential of
the region as part of the decision process, in which spring
geochemistry can be a useful indicator. Further study of
the anomalous springs may be warranted prior to incorpo-
rating source areas into protected land status, where local
stakeholders may want to further explore possible mining
opportunities.
Acknowledgements
Melanie Myden provided field assistance; Glenn Sibbe-
ston from Great Slave Helicopters provided helicopter sup-
port, Canadian Zinc provided accommodation at Prairie
Creek. Funding was provided by Parks Canada and Natural
Resources Canada through the MERA process. Discussions
with Charlie Jefferson helped improve this work. Thought-
ful and thorough reviews of the manuscript were provided
by Bernhard Mayer, David Banks and Patrice de Caritat.
Geological Survey of Canada Contribution Number
20070629.
References
Appello, C.A.J., Postma, D., 1999. Geochemistry, Groundwater and
Pollution. A.A. Balkema Publishers, Rotterdam, Netherlands.
Blusson, S.L., 1968. Geology and Tungsten Deposits Near the Headwaters
of Flat River, Yukon Territory and Southwestern District of Mackenzie,
Canada. Geol. Surv. Canada Paper 67-22.
Brandon, L.V., 1965. Groundwater and Water Supply in the District of
Mackenzie, Yukon Territory, and Adjoining Parts of British Columbia.
Geol. Surv. Canada, Paper 64-39.
Brook, G.A., Ford, D.C., 1980. Hydrology of the Nahanni Karst, Northern
Canada, and the Importance of Extreme Summer Storms. J. Hydrol. 46,
103121.
Canadian Council on Ecological Areas (CCEA), 2006. Ecozones of Canada.
.
Caron, M.-E., 2007. Spring Geochemistry: A Tool for Mineral Explorationin the South Nahanni River Basin, NWT. M.Sc. Thesis, Univ. of Calgary,
Department of Geol. and Geophys., Canada.
Carrillo-Chavez, A., Morton-Bermea, O., Gonzalez-Partida, E., Rivas-
Solorzano, H., Oesler, G., Garcia-Meza, V., Hernandez, E., Morales, P.,
Cienfuegos, E., 2003. Environmental geochemistry of the Guanajuato
Mining District, Mexico. Ore Geol. Rev. 23, 277297.
Coleman, M.L., Shepherd, T.J., Durham, J.J., Rouse, J.E., Moore, G.R., 1982.
Reduction of water with zinc for hydrogen isotope analysis. Anal.
Chem. 54, 993995.
Cox, D.P., Singer, D.A. (Eds.), 1986. Mineral deposit models. US Geol. Surv.
Bull., 1693.
Crandall, J.T., Sadlier-Brown, T.L., 1976. Data on geothermal areas:
Cordilleran Yukon, Northwest Territories, and adjacent British
Columbia. Dept. of Supply and Services and Dept. of Energy, Mines
and Resources, Canada, Contract Number 1SQ5-0136.
de Caritat, P., Kirste, D., 2005. Hydrogeochemistry applied to mineral
exploration under cover in the Curnamona Province. MESA J. 37, 1317.
Deering, M.F., Mohr, E.T., Sypniewski, B.F., Carlson, E.H., 1983. Regional
hydrogeochemical patterns in ground water of northwestern Ohio
and their relation to Mississippi Valley-type mineral occurrences. J.
Geochem. Explor. 19, 225241.
Donnelly, T., Waldron, S., Tait, A., Dougans, J., Bearhop, S., 2001. Hydrogen
isotope analysis of natural abundance and deuterium-enriched
waters by reduction over chromium on-line to a dynamic dual inlet
isotope-ratio mass spectrometer. Rapid Commun. Mass Spectrom. 15,
12971303.
Drever, J.I., 1997. The Geochemistry of Natural Waters, third ed. Prentice
Hall, Upper Saddle River, NJ.
du Bray, E.A., (Ed.), 1995. Preliminary Compilation of Descriptive
Geoenvironmental Mineral Deposit Models. US Geol. Surv. Open-File
Report 95-931.
Eppinger, R.G., Briggs, P.H., Rosenkrans, D., Ballestrazze, V., 2000.
Environmental Geochemical Studies of Selected Mineral Deposits in
Wrangell-St.Elias National Park and Preserve, Alaska. US Geol. Surv.
Prof. Paper 1619.
Eppinger, R.G., Briggs, P.H., Crock, J.G., Meier, Al.L., Sutley, S.J.,
Theodorakos, P.M., 2002. Environmentalgeochemical study of
the Slate Creek antimony deposit, Kantisha Hills, Denali
National Park and Preserve, Alaska. US Geol. Surv. Prof. Paper
1662, pp. 123141.
Epstein, S., Mayeda, T.K., 1953. Variation of18O content of waters from
natural sources. Geochim. Cosmochim. Acta 4, 213224.
Falck, H., Wright, D.F. (Eds.), 2007. Mineral and Energy Resource Potential
of the Proposed Expansion to the Nahanni National Park Reserve,Northern Cordillera, Northwest Territories. Geol. Surv. Canada, Open
File, 5344.
Forster, C., Smith, L., 1988. Groundwater flow systems in mountainous
terrain 2: Controlling factors. Water Resour. Res. 24, 10111023.
Fournier, R.O., 1981. Application of water geochemistry to geothermal
exploration and reservoir engineering. In: Rybach, L., Muffler, L.J.P.
(Eds.), Geothermal Systems: Principles and Case Histories. John Wiley
& Sons, Chichester, pp. 109143.
Friedman, I., 1953. Deuterium content of natural water and other
substances. Geochim. Cosmochim. Acta 4, 89103.
Gabrielse, H., Roddick, J.A., Blusson, S.L., 1965. Flat River, Glacier Lake, and
Wrigley Lake, District of Mackenzie and Yukon Territory. Geol. Surv.
Canada, Paper 64-52.
Gehre, M., Hoefling, R., Kowski, P., Strauch, G., 1996. Sample preparation
device for quantitative hydrogen isotope analysis using chromium
metal. Anal. Chem. 68, 44144417.
Gendzwill, D.J., 1994. Earthquakes and a review of seismicity in theCanadian North. Musk-Ox 40, 3146.
Giblin, A., 2001. Groundwaters Geochemical Pathfinders to Concealed
Ore Deposits. CSIRO Exploration and Mining, Australia.
Gibson, J.J., Prowse, T.D., 2002. Stable isotopes in river ice: identifying
primary over-winter streamflow signals and their hydrological
significance. Hydrol. Process. 16, 873890.
GNWT (Government of Northwest Territories), 2005. A Guide to Mineral
Deposits of the Northwest Territories. Minerals, Oil and Gas Division,
Department of Industry, Tourism and Investment. .
Gordey, S.P., Anderson, R.G., 1993. Evolution of the northern Cordilleran
Miogeocline, Nahanni Map area (105I), Yukon and Northwest
Territories. Geol. Surv. Canada, Memoir 428.
Grasby, S.E., Hutcheon, I., 2001. Controls on the distribution of thermal
springs in the southern Canadian Cordillera. Can. J. Earth Sci. 38, 427
440.
Grasby, S.E., Hutcheon, I., Krouse, H.R., 2000. The influence of water/rockinteraction the chemistry of thermal springs in western Canada. Appl.
Geochem. 15, 439454.
Gulley, A.L., 1993. Rabbitkettle Hotsprings, Nahanni National Park
Reserve, N.W.T: A Hydrogeological Study. M.Sc. Thesis, Carleton
Univ., Ottawa, Canada.
Hamilton, S.M., 1990. The Application of Spring Water Geochemistry and
Hydrogeology to a Non-renewable Resource Assessment of the South
Nahanni River Area, NWT. M.Sc. Thesis, Carleton Univ., Ottawa-
Carleton.
Hamilton, S.M., Michel, F.A., Jefferson, C.W., 1988. Groundwater
geochemistry, South Nahanni resource assessment area, District of
Mackenzie. Geol.Surv. Canada, Paper 88-1E, pp. 127136.
Hamilton, S.M., Michel, F.A., Jefferson, C.W., 1990. CO2-rich ground
waters of the flat river valley, NWT. In: Prowse, T.D., Ommanney,
C.S.L. (Eds.), Northern Hydrology: Selected Perspectives, Proceedings
of the Northern Hydrology Symposium, 1012 July, Saskatoon,
Saskatchewan.Hannigan, P.K., 2006. Introduction. In: Hannigan, P.K. (Ed.), Potential for
Carbonate-hosted Lead-zinc Mississippi Valley-type Mineralization in
Northern Alberta and Southern Northwest Territories: Geoscience
Contributions, Targeted Geoscience Initiative. Geol. Surv. Canada Bull.
591, 940.
Heon, D. (Compiler), 2003. Selwyn Basin metallogeny: an overview of the
significant geological features of a world famous SEDEX basin. Yukon
Geol. Surv. .
Horita, J., Wesolowski, D., Cole, D., 1993. The activitycomposition
relationship of oxygen and hydrogen isotopes in aqueous salt
solutions: I. Vapor-liquid water equilibration of single salt solutions
from 50 to 100 C. Geochim. Cosmochim. Acta 57, 27972817.
Hyndman, R.D., Fluck, P., Mazzotti, S., Lewis, T.J., Ristau, J., Leonard, L.,
2005. Current tectonics of the northern Canadian Cordillera. Can. J.
Earth Sci. 42, 11171136.
IAEA/WMO, 1998. Global Network of Isotopes in Precipitation Database.
.
M.-E. Caron et al. / Applied Geochemistry 23 (2008) 35613578 3577
http://www.ccea.org/ecozones/http://www.iti.gov.nt.ca/miningoilgas/http://www.iti.gov.nt.ca/miningoilgas/http://www.geology.gov.yk.ca/selwyn.htmlhttp://www.isohis.iaea.org/http://www.isohis.iaea.org/http://www.geology.gov.yk.ca/selwyn.htmlhttp://www.iti.gov.nt.ca/miningoilgas/http://www.iti.gov.nt.ca/miningoilgas/http://www.ccea.org/ecozones/8/6/2019 Spring Water Trace Element Geochemistry a Tool for Resource
18/18
INAC (Indian and Northern Affairs Canada), 2001. Petroleum Exploration
in Northern Canada: A Guide to Oil and Gas Exploration and Potential
Chapter 2 Mackenzie Valley, Southern Territories and Interior
Plains. .
ITIA (International Tungsten Industry Association), 2005. About Tungsten
Resources. .
Jefferson, C.W., Spirito, W.A. (Eds.), 2003. Mineral and Energy Resource
Assessment of the Tlogotsho Plateau, Nahanni Karst, Ragged Ranges
and Adjacent Areas Under Consideration for Expansion of Nahanni
National Park Reserve, Northwest Territories. Geol. Surv. Canada,Open File, 1686.
Kelley, K.D., Taylor, C.D., 1997. Environmental geochemistry of shale-
hosted AgPbZn massive sulfide deposits in northwest Alaska:
natural background concentrations of metals in water from
mineralized zones. Appl. Geochem. 12, 397409.
Leybourne, M.I., Goodfellow, W.D., Boyle, D.R., 1998. Hydrogeochemical,
isotopic, and rare earth element evidence for contrasting water-rock
interactions at two undisturbed ZnPb massive sulphide deposits,
Bathurst Mining Camp, N.B., Canada. J. Geochem. Explor. 64, 237261.
Lewis, T.J., Hyndman, R.D., Flck, P., 2003. Heat flow, heat generation, and
crustal temperatures in the northern Canadian Cordillera: thermal
control of tectonics. J. Geophys. Res. 108, 23162334.
Mathews, W.H., 1986. Physiographic Map of the Canadian Cordillera.
Geological Survey of Canada, Map No. 1701A.
Michard, G., 1990. Behavior of major elements and some trace elements
(Li, Rb, Cs, Sr, Fe, Mn, W, F) in deep hot waters from granitic areas.
Chem. Geol. 89, 117134.Miller, W.R., 2002. Influence of Rock Composition on the Geochemistry of
Stream and Spring Waters from Mountainous Watersheds in the
Gunnison, Uncompahgre, and Grand Mesa National Forests, Colorado.
US Geol. Surv. Prof. Paper 1667.
Morrow, D.W., Miles, W.C., 2000. The Beaver Structure: a cross-strike
discontinuity of possible crustal dimensions in the southern
Mackenzie Fold Belt, Yukon and Northwest Territories, Canada. Bull.
Can. Petrol. Geol. 48, 1929.
Mutlu, H., Gulec, N., 1998. Hydrogeochemical outline of thermal waters
and geochemistry applications in Anatoia (Turkey). J. Volcanol.
Geotherm. Res. 85, 495515.
Nelson, S.T., Dettman, D., 2001. Improving hydrogen isotope ratio
measurements for on-line chromium reduction systems. Rapid
Commun. Mass Spectrom. 15, 23012306.
NRCan (Natural Resources Canada), 1995. Canada Permafrost. The
National Atlas of Canada 5th ed. Map No. MCR 4177. .
Ohkuni, T., Sakamoto, F., Kozai, N., Ozaki, T., Yoshida, T., Narumi, I.,
Wakai, E., Sakai, T., Francis, A., 2004. Mechanisms of arsenic
immobilization in a biomat from mine discharge water. Chem.
Geol. 212, 279290.
Okulitch, A.V. (Compiler), 2005. Bedrock Geology, Redstone River, Yukon
Territory, Northwest Territories, 1:1 000 000, Geol. Surv. Canada, Map
No. NP-9/10-G.
ONeil, J.R., Adami, L.H., Epstein, S., 1975. Revised value for the18O
fractionation factor between CO2 and water at 25 C. J. Res. US Geol.
Surv. 3, 623624.
Pellicori, D.A., Gammons, C.H., Poulson, S.R., 2005. Geochemistry and
stable isotope composition of the Berkeley pit lake and surrounding
mine waters, Butte, Montana. Appl. Geochem. 20, 21162137.
Plumlee, G.S., 1999. The environmental geology of mineral deposits. In:
Filipek, L.H., Plumlee, G.S. (Eds.), The Environmental Geochemistry of
Mineral Deposits, Part A: Processes, Techniques and Health Issues.
Rev. Economic Geol. 6A, 71116.
Plumlee, G.S., Logsdon, M.J., 1999. An earth-system toolkit for
environmentally friendly mineral resource development. In: Filipek,
L.H., Plumlee, G.S. (Eds.), The Environmental Geochemistry of Mineral
Deposits, Part A: Processes, Techniques and Health Issues. Rev.
Economic Geol. 6A, 127.
Plumlee, G.S., Smith, K.S., Ficklin, W.H., 1994. Geoenvironmental Models
of Mineral Deposits and Geology-Based Mineral-EnvironmentalAssessments of Public Lands. US Geol. Surv. Open-File Report 94-203.
Rasmussen, K.L., Mortensen, J.K., Falck, H., 2006. Geochronological and
lithogeochemical studies of intrusive rocks in the Nahanni region,
southwestern Northwest Territories and southeastern Yukon. In:
Edmond, D.S., Bradshaw, G.D., Lewis, L.L., Weston, L.H. (Eds.), Yukon
Exploration and Geology 2005. Yukon Geol. Surv. 287298.
Reimann, C., Garrett, R.G., 2005. Geochemical background concept and
reality. Sci. Total Environ. 350, 1227.
Runnells, D.D. (Chairman), 1984. Workshop 3: Hydrochemistry in Mineral
Exploration. J. Geochem. Explor. 21, 129131.
Seal II, R.R., Foley, N.K. (Eds.), 2002. Progress on Geoenvironmental
Models for Selected Mineral Deposit Types. US Geol. Surv. Open File
Report 02-195 (Chapters AL).
Sidenko, N.V., Sherriff, B.L., 2005. The attenuation of Ni, Zn and Cu, by
secondary Fe phases of different crystallinity from surface and ground
water of two sulfide mine tailings in Manitoba, Canada. Appl.
Geochem. 20, 11801194.Siegel, D.I., Ericson, D.W., 1980. Hydrology and water quality of the
coppernickel study region, Northeastern Minnesota. US Geol. Surv.
Water-Res. Invest., 80739.
Sofer, Z., Gat, .J.R., 1972. Activities and concentrations of oxygen-18 in
concentrated aqueous salt solutions: analytical and geochemical
implications. Earth Planet. Sci. Lett. 15, 232238.
Souther, J.G., Halstead, E.C., 1973. Mineral and Thermal Waters of Canada.
Geol. Surv. Canada, Paper 73-18.
Steele, K.F., Dilday, T.F., 1985. Hydrogeochemical exploration for
Mississippi Valley-type deposits, Arkansas, USA. J. Geochem. Explor.
23, 7179.
Stott, D.F., 1982. Lower cretaceous Fort St. John Group and upper
cretaceous Dunvegan formation of the foothills and plains of
Alberta, British Columbia, District of Mackenzie and Yukon
Territory. Geol. Surv. Canada Bull., 328.
UNEP-WCMC (United Nations Environment Program World
Conservation Monitoring Center), 2002. World Heritage Sites Nahanni National Park Reserve, Canada, Northwest Territories.
.
Verplanck, P.L., Nordstrom, D.K., Taylor, H.E., Kimball, B.A., 2004. Rare
earth element partitioning between hydrous ferric oxides and acid
mine water during iron oxidation. Appl. Geochem. 19, 13391354.
Wanty, R.B., Berger, B.R., Tuttle, M.L., Briggs, P.H., Meier, A.L., Crock, J.G.,
2006. Hydrogeochemical Investigations in the Osgood Mountains,
North-Central Nevada. US Geol. Surv. Bull., 2210-B.
Wiken, E.B., 1986. Terrestrial Ecozones of Canada. Ecological Land
Classification, Series No. 19. Environment Canada. Hull, Quebec.
Yukon Geological Survey, 1996. Nahanni River (NTS 105I), GEOPROCESS
File Summary Report, 1:250 000. Yukon Geol. Surv. Open File 2002.
.
3578 M.-E. Caron et al. / Applied Geochemistry 23 (2008) 35613578
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