Spring Water Trace Element Geochemistry a Tool for Resource

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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]


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iver

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Nahanni Karst /Ram Plateau

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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.

3562 M.-E. Caron et al. / Applied Geochemistry 23 (2008) 35613578


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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


10/18


11/18

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.



12/18

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 (


13/18

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.



14/18

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


15/18

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.



16/18

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.



17/18

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.

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