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XXX10.1144/geochem2014-333D.J. Gray etal.

Hydrogeochemistry of the northern Yilgarn Craton


2016

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from http://geea.lyellcollection.org/ at Instituto Geologico Minero y Metalurgico on April 6, 2016
2014-333
Gordon J. Sutton &, Mark C. Pirlo

research-articleThematic set: Tribute to Eion M. Cameron10.1144/geochem2014-333Regional scale hydrogeochemical mapping of the northern Yilgarn Craton, Western Australia: a new technology for exploration in arid AustraliaDavid J. Gray, Ryan R.P. Noble, Nathan Reid,

Thematic set:
Tribute to Eion M. Cameron

Geochemistry: Exploration, Environment, Analysis

Published online February 8, 2016 doi:10.1144/geochem2014-333 | Vol. 16 | 2016 | pp. 100115

Regional scale hydrogeochemical mapping of the northern


Yilgarn Craton, Western Australia: a new technology for
exploration in arid Australia
David J. Gray1*, Ryan R.P. Noble1, Nathan Reid1, Gordon J. Sutton2 & Mark C. Pirlo3
1 CSIRO

Mineral Resources, 26 Dick Perry Ave, Kensington, WA 6151, Australia


of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia
3 Exploration & Environmental Geochemist: www.pirlo.com.au
* Correspondence: david.gray@csiro.au
2 School

Abstract: The northern Yilgarn Craton, with an extensive mineral exploration history and relatively fresh and neutral
groundwaters, was selected to test the utility of regional hydrogeochemical mapping in Australia. The assembled data of
2509 groundwater samples (generally at 48km spacing) are relatively unbiased, allowing robust statistical analysis such as
testing sample types (flowing v. stagnant), contamination, and lithological controls on groundwater characteristics. Lithological indicators were developed to map underlying bedrock through cover. Areas with discrepancies between groundwater
results and previous geological mapping were identified. Where these are areas previously discounted as prospective for
mineral commodities, they may now be re-considered on this basis. Even in well explored parts of this region, this study
identified new areas which may have prospective rocks overlain with a thin (<50m) veneer of granitic material. A large
background data set was produced that has significant benefits for lithological discrimination, mineral exploration, guiding
human and livestock drinking water supplies and environmental management (e.g. mine closure).
Groundwater chemistry can effectively map large-scale lithological changes in these semi-arid environments, and in turn
can reduce uncertainly about the prospectivity of areas within the northern Yilgarn Craton. This should reduce the drilling
and associated costs required to delineate a target. The methods and interpretation developed in this study will enhance
mineral exploration into covered environments as much of the northern two thirds of Australia has similar groundwater
environments. This methodology can be expanded into covered arid terrains worldwide. Additionally, this can be used as
background to improve interpretation of other small scale studies. Improving the exploration potential of other more difficult
regions of Australia will encourage industry exploration in Australia, and provide potential future economic gains.
Keywords: groundwater; geology; mapping; weathering; exploration; geochemistry
Received 11 December 2014; revised 29 October 2015; accepted 4 November 2015

Mineral exploration is becoming increasingly expensive in Western


Australia and throughout the world. Exploration targets are becoming more difficult to find and greater emphasis is being placed on
exploring through deep (>30m) transported cover and into basin
terrains. Groundwater interacting with mineralized rocks can create
a geochemical signature that may be much greater in size than identified from rock geochemistry. This can reduce the required sampling density, assisting cost effective exploration in covered
terrains. Exploration hydrogeochemistry has been advocated for
many areas of the world (e.g. Leybourne & Cameron 2010). The
authors have been developing this technology in Western Australia
(Gray 2001; Gray & Noble 2006; Gray etal. 2011, 2014), while
Giblin (1994), Kirste etal. (2003), Pirlo & Giblin (2004) and de
Caritat etal. (2005) have also pursued these methods in Australia.
This northern Yilgarn study was a test of concept for broad
scale hydrogeochemistry, with potential for lithological mapping,
establishment of environmental background and mineral exploration in other areas, especially outside recognized mineralization
belts. The area selected within the Archaean-aged Yilgarn Craton,
hosts numerous Ni, Au and U ore systems, as well as several
VHMS Zn (Cu, Ag) deposits. Hydrogeochemical studies also provide information on rock weathering to benefit exploration effectiveness in regolith-dominated terrains.
The sampling is relatively unbiased with regards to geology and
or mineralization. This enabled various other testing to be done,
including comparison of pumped v. stagnant wells and bores,

how to measure contamination in stagnant wells, and which


elements are affected. Such metrics may have value when examining other databases based on similar sampling methodologies.
Specific applications of the use of groundwater chemistry in
exploring for particular commodities in Australia are discussed in
other papers (e.g. U by Noble etal. 2011, VHMS by Gray etal.
2014) with initial developments described in Gray etal. (2009,
2014). This paper discusses the methods used to develop and interpret large scale regional hydrogeochemical databases. We also
briefly discuss the utility of groundwater for lithogeochemical
mapping, and the various statistical and mathematical approaches
utilized to develop robust groundwater applications that can be
relatively easily applied elsewhere in Australia or the world.

Geological and groundwater characteristics of


the Yilgarn Craton
The >2500Ma Yilgarn Craton is located within the SW of Australia
(Fig. 1). The geology of the northern Yilgarn Craton is comprised
of variably distributed Archaean-aged granites and greenstones
(dominantly mafic volcanic rocks, Fig. 2). The greenstones occur
in a series of belts including the Norseman-Wiluna, Yandal,
Duketon, Dingo Range, Meekatharra, Windimurra, and Gum
Creek Belts (Myers & Hocking 1998; Morris & Sanders 2001).
Cassidy etal. (2006) summarize the tectonic evolution of the
Yilgarn Craton. The northern Yilgarn is split by a continental

2016 The Author(s). Published by The Geological Society of London for GSL and AAG. All rights reserved. For permissions: http://www.geolsoc.org.uk/
permissions. Publishing disclaimer: www.geolsoc.org.uk/pub_ethics

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Hydrogeochemistry of the northern Yilgarn Craton

101

Fig. 1. (a) Simplified geology map of the


Yilgarn Craton, SW Australia (GSWA
2014), with continental divide between
Indian Ocean and internal drainage
shown; (b) Rainfall (mm) isohyets
(Australian Bureau of Meteorology,
19611990).

Fig. 2. Geology (GSWA 2014), main


towns, mines and water catchments of
the northern Yilgarn Craton. The broad
blue line denotes the continental divide
between Indian Ocean and internal
drainage, and the thin blue lines are the
main drainage systems. Greyed areas are
the main saline playas.

divide; to the east is the Southern Cross Domain and to the west is
the Murchison Domain, both part of the Youanmi Terrane, which
in turn is part of the Eastern Goldfields Superterrane. Both
Domains in this area have granitic rocks and granitic gneiss associated with extensive NE trending, elongate greenstone belts
(Williams 1975; Myers 1997). The granitic rocks comprise granodiorite-monzogranite and deformed and metamorphosed monzogranites (Cornelius etal. 2008). The greenstones generally
comprise mafic and ultramafic volcanic rocks underlain by quartzite, banded iron formation and minor felsic volcanics. The
Windimurra Belt (between Mt Magnet and Sandstone; Fig. 2) is
different from the other greenstone belts in the sampling area. It is
a layered gabbroic intrusive containing vanadiferous and titaniferous magnetite bands.
The Yilgarn Craton is commonly deeply weathered (20100m).
Surficial aquifers are mainly unconfined, with the water-table
commonly 1060m below surface in the southern half and 235m
in the north. Numerous researchers have discussed the Menzies
Line (Fig. 3), a groundwater/soil/botanical divide running approximately EW at 29.5S (e.g. Butt etal. 1977). South of this line, the
dominant flora are generally Eucalyptus (gum) species (often in
mallee form in more arid areas), and soils commonly contain calcite (CaCO3; Chen etal. 2002). To the north, Acacia (wattle) or
Triodia (spinifex) species commonly dominate and soils are carbonate-poor (Anand & Butt 2010).
This surface differentiation is also consistent with major
groundwater differentiation: south of the Menzies line groundwaters are commonly acidic and saline to hypersaline (Fig. 3;
Commander 1989); whereas to the north groundwaters are neutral
to alkaline and generally fresh, trending to saline in the main valley
floors (Gray 2001). This northern region was selected for the
hydrogeochemical mapping study, as it has generally fresh waters,
without the extreme variation in acidity (pH 38) and high salinity

(commonly >30
000
mg/L) of the southern Yilgarn Craton.
Additionally, the north Yilgarn has ubiquitous access to farm
bores, as well as similarities to other central Australian environments. Within the northern Yilgarn Craton there is some salinity
differentiation: the thin blue lines in Figure 2 show the boundaries
of the major water catchments: most samples from the upstream,
higher elevation, parts of the catchment areas are fresh; compared
with the higher salinity along the valley floors. The NS broad blue
line at approximately 119E represents the continental divide
between drainage to the Indian Ocean, and, to the east, internal
drainage to the Officer and Eucla Basins.

Sampling and field treatments


Shallow groundwater samples (n=2509) were collected across the
northern Yilgarn Craton (Fig. 4) from wells and bores used for
livestock and human consumption, with the majority of samples
coming from groundwater with water tables within 10m of the surface. The most effective collection method (1457 samples), was
directly from actively pumping farm (windmill, solar) bores, as
close to the pumping stem as possible, to avoid any possible intrain contamination or precipitation. Another 1052 groundwater
samples were collected using a flow-through bailer (fitted with
one-way valves) due to abandonment or access difficulties. Where
possible, bailed samples were collected c. 5m below the water
table, but on occasion there was less than 5m of water available,
and water was sampled from shallower depths.
The water sample is being brought upwards from depth and will
interact with the atmosphere. Addition of atmospheric O2 will
commonly cause precipitation of colloidal Fe hydroxide, which
could then lead to co-precipitation of metals of interest. Degassing
of CO2 will raise pH and also effect element solubilities.
These issues are minor for these surficial groundwaters which are

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102

D.J. Gray etal.

Fig. 3. Modelled groundwater salinities


of the Yilgarn Craton (modified from
Commander 1989).

Fig. 4. Groundwater samples in the


northern Yilgarn Craton. The areas
highlighted with the thick red line are
anomalous for various parameters and
discussed in the text. Dashed areas
are also noted as being potentially
anomalous.

generally neutral pH and moderate Eh (>0mV), low (commonly


<0.01mg/l) dissolved Fe and Mn and with low CO2 (commonly
<0.01atm partial pressure). Even so, field protocols were designed
such that filtering and storage of waters are initiated immediately
after sampling, so as to minimize any such issues.
Standard logging protocols were developed. The depth of the
water table was recorded with a dip meter. Waters were analysed
for pH, temperature, conductivity and oxidation potential (Eh; corrected to Standard Hydrogen Potential; ZoBell 1946) at the time of
sampling. Estimated measurement errors are: pH 0.05; temperature 0.5C; conductivity 5%; Eh 20mV. An unfiltered sample
was collected, with overfilling to remove all air, for later HCO3
analysis by alkalinity titration in the laboratory. Comparisons of
laboratory alkalinity values against immediate field titrations for
20 differing sites demonstrated good linear calibration between
these methods, and laboratory titration was chosen as the preferred
time efficient and precise technique. High density polyethylene
(HDPE) bottles were used, with filtering to 0.45m pore size
(Supor-450 47mm 0.45m Membrane Filter). Previous investigations (Noble & Gray 2010) demonstrated highly correlated
results for 0.1 v. 0.45m for most elements, with the exception of

Fe and Al. At each site the filtration equipment was thoroughly


rinsed with deionized water, and a new filter paper inserted.
Approximately 100mL water was filtered and collected (with rinsing) for anion analysis. Subsequently, an additional 100mL was
filtered and then collected (with double rinsing) for ICP analysis.
Concentrated nitric acid (69%) of ultra high purity grade
was added to these samples in the laboratory to approximately
0.2% v/v.
Carbon sachets (comprised of 1g of activated carbon in a nylon
mesh) were placed in a 1000mL bottle with 10g NaCl to provide
an approximate ionic balance between samples irrespective of initial water sample salinity. The solutions were agitated for at least
4 days, at which point the carbon was extracted by aqua regia for
low level (ng/L) detection of Au, Ag and PGE (Platinum Group
Elements; Chemical analyses section).

Groundwater analyses
Chemical analyses
A set volume of the sealed, unfiltered sample was titrated for
HCO3 with a known concentration of acid (e.g. 0.01 M HCl) to an

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Hydrogeochemistry of the northern Yilgarn Craton


endpoint of pH
=
4.3 at CSIRO Laboratories in Kensington,
Western Australia. Direct comparisons of field and laboratory
alkalinity analyses for 44 sites showed a direct linear correlation
between analyses for these shallow groundwaters. Major anions
(Cl, SO4, Br, F and NO3) were analysed using the filtered sample
by Ion Chromatography (IC) at CSIRO Laboratories in Kensington,
Western Australia. The IC equipment used was a Metrohm modular IC using an acid re-generated suppressor, MetroSep A Supp5
column, a carbonate/bicarbonate eluent (32mM Na2CO3 and
10mM NaHCO3) and a conductivity detector. A sample split was
sent to CSIRO Land and Water Laboratory in Adelaide for analysis of Dissolved Organic Carbon (DOC) and PO4.
Major elements Al, B, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Na, P, S,
Si, Sr and Zn) were analysed by Inductively Coupled Plasma
Optical Emission Spectroscopy (ICP-OES) at CSIRO Land and
Water Laboratory in Adelaide, SA. Trace elements (Ag, As, Ba,
Cd, Ce, Co, Cr, Cu, Dy, Er, Eu, Ga, Hf, Ho, La, Lu, Mo, Nb, Nd,
Ni, Pb, Pr, Rb, Sb, Sc, Sm, Sn, Sr, Ta, Th, U, V, W, Y, Yb, Zn and
Zr) were analysed by Inductively Coupled Plasma Mass
Spectrometry (ICP-MS): the first quarter of the samples were analysed at Geoscience Australia, Canberra, and the rest at CSIRO
Land and Water in Adelaide, SA. Many samples were still below
detection for REE, Ag, Cd and Ni. Detection limits for ICP analyses are affected by salinity, with more saline samples having
higher detection limits due to increased dilution requirements
(Table 1). Initial batch effects were removed with increases of
reported detection limits (see 4.3 and 4.4 below).
Dissolved Au, Ag and PGE were below detection in groundwater samples, hence the use of an activated carbon sachet to preconcentrate these critical pathfinders. The carbon analysis was
performed by a commercial laboratory (Bureau Veritas in
Canningvale, WA). The activated charcoal was ashed, and the
residue dissolved in aqua-regia. The solution was analysed by
ICP-MS for Au, Pt, Pd, and Ag. Laboratory investigations have
indicated that using this preconcentration system will enable successful analyses of waters for Au, Ag and PGE at low concentrations, though at a lessened accuracy than via standard analyses.
Calibration of the method was obtained by shaking standards of
varying concentrations, and in varying salinities, with activated
carbon.

Solution modelling
Equilibrium activity diagrams were derived using The
Geochemists Workbench (Bethke 2007). Solution chemical speciation and degree of mineral saturation are determined as
Saturation Indices [SI; log10[(Ion Activity Product)/(Solubility
Constant)] from the solution compositions using the program
PHREEQE (Parkhurst etal. 1980). If the SI for a mineral is within
the zero range the water is in equilibrium with that mineral, under
the conditions specified. The zero range is estimated for every
mineral based on stoichiometry, thermodynamic accuracy and
analytical issues; ranging from 0.2 to 0.2 for major element minerals such as halite or gypsum to (for example) 1.5 to 1.5 for a
complex minor element mineral such as carnotite (KUO2VO4).
Where the SI is below the zero range, the solution is under-saturated with respect to that mineral, so that, if present, the phase may
dissolve. If the SI is greater than zero the solution is over-saturated
with respect to this mineral, which could potentially precipitate
from solution.
Such determinations only specify possible reactions, as kinetic
constraints may rule out reactions in shallow environments at low
temperature and pressure (i.e. approximately 25C/1atm). For
example, waters are commonly in equilibrium with calcite, but
may become over-saturated with respect to dolomite, due to the
slow rate of precipitation of this mineral (Drever 1982). However,

103

this method still provides understanding of the thermodynamic


constraints on solution processes at a site. This assists in determining whether the spatial distribution of an element is correlated with
geological properties such as lithology or mineralization, or
whether they are related to weathering/environmental effects. For
example, if Ca distribution is controlled by equilibrium with gypsum in all samples, then the spatial distribution of dissolved Ca
will reflect SO4 concentration alone and have no direct exploration
significance.

Quality control
The quality control of analyses was monitored by analysing laboratory standards (1 in 20 samples), blanks (1 in 20) and duplicate
samples (1 in 15 samples for anion and alkalinity analyses, 1 in
20 samples for ICP-MS and ICP-OES). Both the Geoscience
Australia (Canberra) and CSIRO (Adelaide) laboratories were used
over this time for ICP-MS analyses, as well as having some of the
equipment change due to upgrades. Therefore, special care was taken
in the cross laboratory QA/QC. In addition to the duplicates within
the north Yilgarn samples, duplicates from previous projects were
submitted as another check. Using duplicates, blanks and standards
results, the errors for each element were calculated as % difference
errors, half relative difference errors and 95% confidence errors on
the batch (Stanley & Lawie 2007). The errors are defined as:
% difference error =
( assay1 assay2 ) /maximum ( assay1 or assay2 ) 100
Half relative difference =
( assay1 assay2 ) / ( assay1 + assay22 ) 100

95% confidence = 1.96

n
Where 1.96 is the 95th percentile of a normal distribution with a
mean value of 1, is the standard deviation of all assay1-assay2
values, and n is the number of duplicates. Differences were calculated for each duplicate pair then a 95% confidence error was calculated on these differences, as with Gray etal. (2009). The standard
errors were the 95% confidence of all replicates. The standard
errors were used to determine analytical precision and, the duplicate errors determined sample heterogeneity. Elements with errors
less than 10% were acceptable, whereas those greater than 10% and
with greater than 2 times laboratory detection limit were investigated in more detail to ensure a reliable detection limit (as below).

Determination of sample concentration errors


The errors determined from the duplicate analyses, standards and
blanks were used to determine the upper confidence limit for data
interpretation for each element (Table 1), on the principle that all
values below the greatest error value are noise in the data. Filtering
the data to these higher values reduced the noise component and
smoothed the data. For example, the laboratory quoted detection
limit for As was 0.01g/L; however, from the various batches and
laboratories the duplicate, standard and blank errors were 0.76,
0.14, 0.19, 0.42 and 0.34g/L. Therefore, the maximum error of
0.76g/L was rounded to a 1g/L confidence limit, to ensure robust
interpretation of any concentration differences between sites. This
determination was done for all minor and trace elements (Table 1).

Data treatment and development


Pumping v. stagnant wells or bores
For consistency and comparability, groundwater sampling and
field treatment protocols need to be defined and documented.

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104

D.J. Gray etal.

Table 1. Summary statistics and percentiles for groundwaters of the north Yilgarn Craton. Below detection: Dy, Er, Eu, Gd, Hf, Ho, Lu, Nb, Pr, Sc, Sm,
Ta, Tb, Te, Th, Ti, Tl, Yb and Zr
Name

Units

TDS
pH
Eh
HCO3
F
Cl
Br
NO3
SO4
PO4
DOC
Ca
K
Mg
Na
Al
B
Fe
Si
Sr
Mn
Li
V
Cr
Co
Ni
Cu
Zn
Ga
Ge
As
Se
Rb
Y
Zr
Mo
Cd
In
Sn
Sb
Ba
La
Ce
Pr
Nd
Hf
Ta
W
Tl
Pb
Th
U
Au
Pt
Pd
Ag

mg/L
mV
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
ng/L
ng/L
ng/L
ng/L

Method

No. Values

Confidence Limit

Median

Std Dev#

Min

Max

25th Per.

75th Per.

95th Per.

Field meter
Field meter
Titration
IC
IC
IC
IC
IC
Auto Analyser
TP
ICP-OES
ICP-OES
ICP-OES
ICP-OES
ICP-OES
ICP-OES
ICP-OES
ICP-OES
ICP-OES
ICP-OES
ICP-OES
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS
ICP-MS/C
ICP-MS/C
ICP-MS/C
ICP-MS/C

2463
1965
1828
1672
2387
2459
1884
1453
1669
1647
1647
1979
1979
1979
2210
612
1668
1072
1673
2458
1284
2158
1658
1624
1635
1642
1660
1660
494
465
2450
441
2440
1244
1406
1966
1577
505
1661
1212
1671
1412
1429
947
949
1300
1413
2147
413
1587
993
1966
2368
2411
2312
2264

0
0.02
20
2
0.14
10
0.1
1
8
0.04
1
2
2
2
5
0.01
0.1
0.01
1
0.05
0.005
2
5
1
0.5
3
5
10
0.2
1
1.5
2
5
0.2
1
2
0.5
0.2
1
0.8
2
0.2
0.2
0.2
0.2
1
0.5
2
0.5
1.2
1
2
3
4
4
50

1576
7.6
354
200
0.8
640
2.4
59
192
0.05
2.5
73
20
59
378
0.005
0.9
0.005
35
0.8
0.0025
2
15
0.5
0.25
1.5
10
30
0.1
0.5
0.75
4
15
0.1
0.5
4
0.25
0.1
0.5
0.4
52
0.1
0.1
0.1
0.1
0.5
0.25
1
0.25
0.6
0.5
4
1.5
2
2
25

2910
0.5
57
95
2.6
1477
3.2
45
452
0.1
2.2
89
46
111
853
0.030
1.0
0.15
9
1.2
0.05
19
23
9
0.3
5
56
212
0.0
0.1
58
2.5
25
0.1
0.1
16
0.1
0.0
0.5
1.3
70
0.2
0.3
0.0
0.2
0.0
0.0
1.0
0.0
2.2
0
35
9
3
1.2
237

59
5.5
54
4
0.07
5
0.1
0.5
4
0.02
0.5
3
1
1
9
0.005
0.05
0.005
0.5
0.025
0.0025
1
2.5
0.5
0.25
1.5
2.5
5
0.1
0.5
0.75
1
2.5
0.1
0.5
1
0.25
0.1
0.5
0.4
1
0.1
0.1
0.1
0.1
0.5
0.25
1
0.25
0.6
0.5
1
1.5
2
2
25

80145
10.9
572
775
73.8
38310
47.2
1106
12200
1.02
48.5
868
1660
2887
24004
0.5
26
4.3
57
16.8
0.99
280
290
310
8
120
925
4970
0.4
2
2795
24
375
2.8
2
318
3.5
0.2
14
44
2542
5.2
12
0.4
7.2
1
0.5
26
0.5
82.8
0.5
696
357
160
48
8200

940
7.4
317
140
0.4
340
1.4
42
112
0.02
1.2
47
12
36
212
0.005
0.6
0.005
28
0.5
0.0025
1
10
0.5
0.25
1.5
5
20
0.1
0.5
0.75
2
10
0.1
0.5
2
0.25
0.1
0.5
0.4
38
0.1
0.1
0.1
0.1
0.5
0.25
1
0.25
0.6
0.5
1
1.5
2
2
25

2809
8.0
385
260
1.2
1260
4.2
81
312
0.07
3.4
115
34
103
714
0.005
1.3
0.02
40
1.3
0.005
12
30
1
0.25
1.5
25
60
0.1
0.5
3
4
30
0.1
0.5
10
0.25
0.1
0.5
0.4
72
0.1
0.1
0.1
0.1
0.5
0.25
1
0.25
0.6
0.5
14
1.5
2
2
25

6392
8.5
436
360
2.2
3200
8.2
129
717
0.20
5.7
261
77
234
1730
0.04
2.5
0.13
46
3.0
0.03
42
60
7
0.25
3
80
200
0.1
0.5
7.5
8
65
0.2
0.5
28
0.25
0.1
0.5
0.4
126
0.1
0.1
0.1
0.1
0.5
0.25
1
0.25
1.2
0.5
64
6
2
2
150

Samples from routinely pumping windmills, solar or other pumping bores were distinguished as flowing, whereas non-pumping
wells or bores were defined as stagnant. Presumably, continually pumping windmills provide a better representative sample
than stagnant wells. However, it may still be a compromised
sub-sample - for example, in this survey the observed Zn concentrations consistently greater than 10g/L could be partially due to

minor contamination from flow through galvanized piping. A bigger issue is the bailing of water from stagnant wells and bores.
Not using these water samples causes broad gaps in the mapping
area. Testing to see if bailed samples are useable and clarifying
how to robustly incorporate these samples is critical for this survey, and additionally may have value in dealing with historical
data.

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Hydrogeochemistry of the northern Yilgarn Craton

105

Fig. 5. Probability plot comparison


of ranked concentration v. n score
for flowing and stagnant samples,
showing distinct population differences.
Separation of the lines indicates
differences in the types of samples. Both
Mn and PO4 have different distributions
in the stagnant water samples compared
to the flowing water samples.

There are major time and logistic issues in purging remote bores
and wells. Additionally, purging of monitoring wells can significantly affect sample quality and may itself lead to non-representative groundwater samples (Barcelona etal. 1994; Nielsen &
Nielsen 2006). A traditional purging strategy is the removal of a
fixed, but arbitrarily defined, number of well volumes. This typically involves purging 35 well volumes but does not account for
variation in site-specific hydrogeology, well response, purging rate
or provide independent chemically-based confirmation of when a
representative groundwater sample enters the well (Barcelona
etal. 1994; Nielsen & Nielsen 2006). The well may be hydraulically over-purged and dewatered, causing aeration of the formation and increased sample turbidity. Such issues will be particularly
marked in purging 3+ well volumes of a well several metres diameter and 10s of metres deep.
The north Yilgarn terrain is primary an uncovered, deeply
weathered environment and the surficial aquifer being sampled in
this study is un- or weakly- pressurized. With predominantly horizontal groundwater flow and uncased well walls, there will be a
significant component of lateral flow through the well. Use of a
bailing system, preferably to 5m below the water table, may still
derive a useful sample indicative of the surrounding groundwater.
This procedure has been used for stagnant wells and bores in this
study, though (as discussed below) with statistical comparisons
against regularly pumping sources.
A number of processes within a stagnant well or bore may
modify the original signal, including degassing, interaction with
well linings or metal infrastructure, or organic contamination. It
may be difficult to totally separate these effects, and for the purposes of this discussion, these are all included as contamination.
Intuitively, we expect that severely contaminated samples (e.g.
dead animals in wells) should be used with extreme caution,
whereas wells that have been routinely pumped until the week
before sampling may offer good results for many elements. This
leads to the contention that stagnant samples cannot be treated as
a single sample set, and if stagnant samples are used it is critical
to find a way to characterize and group these samples i.e. a contamination index. As described below, combining empirical evidence with an understanding of the chemical changes occurring in
such wells and bores enabled us to develop metrics for contamination in stagnant samples, which when interpreted conservatively
gives a data-set for which the sampling errors are minor relative to
the differences in original chemistry.
Visual logging of the condition of the site and visual and smell
testing gives important information and we integrated this into a
field logging scheme. Comparative concentration distributions of
flowing and stagnant sample sets were examined by plotting the
ranked concentration (or, where appropriate, log concentration) v.
of each element v. the N-score values (i.e. z-scores from a standard
normal distribution (mean=0 and a standard deviation=1) using in
IoGas (IoGlobal 2011). Some specific elements, such as Mn or P
(measured as PO4; Fig. 5), differed greatly between flowing and

stagnant samples (and were used as contamination parameters).


For example, PO4 is significantly higher in stagnant, relative to
flowing, samples (Fig. 5), with 45% of the stagnant samples having PO4 contents greater than the 98th percentile level for flowing
samples.
The most strongly (orders of magnitude) enriched solutes in
stagnant samples (particularly when visibly discoloured or
smelly) were DOC, PO4 (expected to be from biological sources),
Mn (possibly reductive leaching), Fe and Zn (possibly from various sources including metallic materials). Not surprisingly, there
are inter-relationships between their chemistries in contaminated
samples (Figs 6 and 7). Dissolved Fe and Mn can be used in this
manner for this sample set as they are commonly low in these
surficial groundwaters (for flowing samples: Fe median
0.004mg/L, mean 0.037mg/L; Mn median 0.002mg/L, mean
0.010mg/L).
Samples observed in the field to be contaminated (based on the
state of the well and/or the colour and smell of the samples) had a
number of clear differences:
-Significantly higher in at least one of DOC, PO4, Mn, Fe and
Zn;
-Significantly lower in various elements expected to be sensitive
to reduction, such as U and Cr, and NO3 and SO4 (when plotted
relative to Cl).
Other parameters also showed variation, such as Eh which was
commonly lower in highly contaminated samples, and bicarbonate which trended towards higher values in contaminated samples (and weakly correlated with DOC). However, these two
parameters were not useful in robustly determining contamination, as the contamination effects were less than the background
variation.

Determination of contamination values and


factors
DOC, PO4, Mn, Fe and Zn were used to create a contamination
value (CV):
P
OC
Fe
Mn
Zn

, log10
, log10
, log10
CV = Mean log10
, log10

0.277
6.94
0.234
0.059
0.546

(all elements in mg/L).

The denominators used for each of the variables are the 98th percentile for each variable in the flowing bore dataset. As shown
below, the CV was used to split the samples into 6 contamination
factor (CF) classes (% shown is the proportion of each CF class of
the entire dataset):
CF 1: Flowing bores (all other CF groups are bailed samples) 58%
CF 1.8: CV < 0.8 (bailed, uncontaminated) 9%
CF 2.2: 0.8 < CV < 0.417 (bailed, very slightly contaminated)
12%
CF3: 0.417 < CV < 0.1 (bailed, slightly contaminated) 9%

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106

D.J. Gray etal.

Fig. 6. Dissolved PO4-P v. organic


carbon for flowing and stagnant samples
of northern Yilgarn groundwaters,
showing distinct population differences.
Stagnant samples are distinguished
based on available field logging. Dashed
lines represent 98 percentile lines for the
flowing samples.

Fig. 7. Dissolved Mn v. Fe for flowing


and stagnant samples of northern
Yilgarn groundwaters, showing distinct
population differences. Stagnant
samples are distinguished based on
available field logging. Dashed lines
represent 98 percentile lines for the
flowing samples.

CF4: 0.1 < CV < 0.3 (bailed, contaminated) 10%


CF5: 0.3 < CV (bailed, highly contaminated) 2%

The CF 1 and 1.8 Groups had very similar probability distributions


for almost all elements (e.g. Figs 8 and 9). The CV cut-off of

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Hydrogeochemistry of the northern Yilgarn Craton

107

Fig. 8. Contamination factor


probability plot split of groundwater U
concentrations. CF classes 1, 1.8, and 2.2
have similar probability populations and
therefore unaffected by contamination,
whereas classes 3, 4 and 5 are culled
from the U data set. Data is also
represented as boxplots: median (black
line), mean (black dot), quartiles (1st
and 4th whiskers), outliers (circles) and
extreme outliers (triangles).

Fig. 9. Contamination factor


probability plot split of groundwater As
concentrations. The various CF classes
were not statistically distinguished.
Arsenic data is also represented as
boxplots as for Figure 8.

0.417 between CF Classes 2.2 and 3, is equal to the 98% percentile value for CV in the flowing bore dataset.
Probability plots were prepared for all elements, coloured by CF
(e.g. Figs 8 and 9). For each element, the probability line for each
CF group were compared with the CF 1 line and culled if the variation was visually significant. Thus, for example, the CF 3, 4 and
5 groups showed probability lines well below that for CF 1 for
dissolved U (Fig. 8) and U data was deleted for these CF groups.
Data for each element that was significantly different from the CF1
population were culled (Table 2). Although this technique should
work well in most instances, some of the high values removed
particularly for Zn, Mn and Fe could be natural. In essence, we
have taken the conservative decision to risk some loss of the highest anomalous Fe, Mn etc values in the stagnant samples, rather
than include any erroneous results caused by contamination. As
more than half the sample set is the flowing samples (CF1), this
will have little effect on the threshold for anomalous values. Such
differentiation is possible as this data is relatively unbiased (not
just sampling over ore deposits). This methodology can be adapted
for other hydrogeochemical surveys.

Element excess and depletion


Using element ratios (compared to Cl or Na), some data were
observed to be in excess or deficit. The ratio distance away from a
standard sea water (SW) line (i.e. the compositions of the ions if
sea water were diluted or concentrated by evaporation) was determined, and provided a numerical measurement of the excess or
depletion. Element ratios discussed in this paper are Sr with respect
to Ca (Fig. 10), Rb with respect to K, K with respect to Na, and
SO4 with respect to Cl.

Table 2. Influence of contamination on each measured component, i.e.


those with only CF Class 1 kept are the most influenced by contamination,
whereas up to CF Class 5 kept indicates the whole data set was used
Element
DOC
Al
B
Ba
Co
Cr
Cu
Eh
HCO3
Mn
Ni
NO3
Pb
PO4
Sb

CF Kept

Element

CF Kept

Element

CF Kept

1
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8

Si
SO4
V
Zn
Fe
pH
U
Mo
REE
Sn
Au
Br
Ca
Cd
Cl

1.8
1.8
1.8
1.8
2.2
2.2
2.2
3
3.
3
4
4
4
4
4

F
K
Mg
Na
Pd
Rb
Sr
TDS
W
Ag
As
Li
Pt

4
4
4
4
4
4
4
4
4
5
5
5
5

The formulas listed below (all in mg/L, except Rb in g/L) were


derived so as to robustly measure deviation from the sea water line
for the specific ion pair. Thus, for KNaSW, the 0.0363 value is the
K:Na ratio in sea water. Sea water ratios are used, as there is a
major input of sea water salt into the Yilgarn Craton, presumably
as aerosols (McArthur etal. 1989). Using the different calculation
methods for lower ion concentrations minimizes skewing the calculated indices due to analytical errors close to detection limits. At
higher concentrations these become a ratio difference (Fig. 10):

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108

D.J. Gray etal.

Fig. 10. Dissolved Sr v. Ca for North


Yilgarn Craton groundwaters, coloured
by SrCaSW range.

Fig. 11. Example of elemental index


generation for dissolved U. The base10
logarithm of uncontaminated classes 1,
1.8 and 2.2 (Fig. 8) was incorporated and
then scaled between 0 and 1.

KNaSW = [2 x (K 0.0363 x Na)]/[0.0363 x (Na + 500)] Na <


500mg/L
= [K 0.0363 x Na]/[0.0363 x Na] Na 500mg/L
SO4ClSW = [2 x (SO4 0.1396 x Cl)]/[0.1396 x (Cl + 500)] Cl
< 500mg/L
= [SO4 0.1396 x Cl]/[0.1396 x Cl] Cl 500 mg/L
SrCaSW = [2 x (Sr 0.0195 x Ca)]/[0.0195 x (Ca + 20)] Ca <
20mg/L
= [Sr 0.0195 x Ca]/[0.0195 x Ca] Ca 20mg/L
RbKSW = [2 x (Rb 0.306 x K)]/[0.306 x (K + 20)] K <
20mg/L
= [Rb 0.306 x K]/[0.306 x K] K 20mg/L
e.g. for Ca > 20mg/L
-SrCaSW = 2 means the Sr/Ca sample ratio is 3 x sea water
-SrCaSW = 1 means the Sr/Ca sample ratio is 2 x sea water
-SrCaSW = 0 means the Sr/Ca sample ratio is equal to that of sea
water
-SrCaSW = 0.5 means the Sr/Ca sample ratio is half that of sea
water
-SrCaSW = 0.75 means the Sr/Ca sample ratio is one quarter
that of sea water
-SrCaSW = 0.95 means the Sr/Ca sample ratio is one twentieth
that of sea water

This interpretation is visually indicated in a plot of Sr v. Ca (Fig.


10), with the data points classified according to the SrCaSW index.
Red dots are at and above the Sr:Ca sea water line and are considered to have a high Sr:Ca ratio. In contrast the blue triangles are
very low in Sr, relative to Ca, and have a high Ca:Sr ratio.

5.4 Elemental indices


Each element concentration was scaled from 0 to 1 based on the
0.1th and 99.9th percentile of the data (if normal distribution) or of
the logged data (if log normal distribution, Fig. 11). There are
some detection issues with this process as some elements are
below detection for many of the samples. In this instance the detection limit was set as the zero value for the index. This will skew the
normal (or log normal) distribution at the low end.

Single element and multi-element indices


A number of elements dissolved in groundwater are useful in discriminating lithologies in the area. For example, dissolved U is higher
over granites, and V and Cr concentrations higher on basic rocks.
However, use of multielement indices gives better lithological discrimination. Given the observed V, Cr enrichment in basic lithologies
in greenstone belts, and of U in granites a lithological index was calculated to test discrimination of greenstone from granitic lithologies:
Lithol 1 = V + Cr 2 U

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Hydrogeochemistry of the northern Yilgarn Craton

109

Fig. 12. Groundwater salinities (TDS)


in the northern Yilgarn Craton in upland
areas only (MrVBF cutoff of 5.6). The
highlighted areas denote upland zones
with significant saline groundwaters.

Other elemental indices have been developed as mineral exploration tools. These are used to show the presence of weathering
sulphides, Fe-rich sulphides, Ni-rich sulphides and other commodities such as Au and U (Gray & Noble 2006; Gray etal. 2009,
2014; Noble etal. 2011).

Mapping of data and lithological differentiation


Following the data treatment described above, the various element
concentrations, ion ratio indices, and saturation indices were plotted overlain on the geological mapping of the Yilgarn Craton (e.g.
Fig. 12). As will be described, a number of differing parameters
closely matched the underlying geology and/or were effected by
faults and geological contacts. In addition, specific areas showed
anomalous groundwater parameters, and these will be highlighted
(Fig. 4), and discussed further in the text. These anomalous areas
were commonly identified using multiple parameters, strengthening the interpretation.

Statistical methods
The groundwater measurements together with the specified rock
types were used to fit various models that identified the geology
using the groundwater measurement data. There were 11 rock
types as mapped by Geological Survey of Western Australia
(GSWA 2014), which were split into two broad classes, referred to
as Greenstone and Granite (using the GSWA nomenclature), as
follows:
Greenstone rock types: mafic intrusive, mafic volcanic,
ultramafic volcanic, mafic volcanic, meta mafic, sedimentary siliciclastic.
Granite rock types: felsic volcanic, granitic, meta felsic
intrusive, protolith unknown, mixed (Felsic rocks were
grouped with the Granite rock types.)
This was a very broad distinction, but is a useful concept. If all 11
categories were treated separately, some categories contained too
few sites for model identification. Details of the datasets, methods
and statistical programming are found in Sutton etal. (2010). To
create a model that distinguished between the two classes, binomial Generalized Linear Models (GLM) were used. The response
variable is a zero-one variable, with Granite denoted 0 and
Greenstone denoted 1. The model provides a fitted value between
zero and one, which estimates the probability that a particular site
is Greenstone, based on the analyte groundwater chemistry at that
site. Initially, a binomial GLM was fitted using all sites and 35
analytes. This gave a baseline on the expected error rate that could
be achieved. A model was then fitted using a forward-backward
selector to select the analytes to include in the binomial GLM,
based on minimising the Akaike information criterion (Sutton

etal. 2010). By this method all samples were allocated to one of


the two geological groups.

Slope analysis
Geology (GSWA 2014), magnetics and gravity (Geoscience
Australia 2009), radiometric (Geoscience Australia 2009), drainage (GSWA 2014) and Multi-resolution Valley Bottom Flatness
(MrVBF; Gallant & Dowling 2003) data sets were used for maps
and interpretation. The MrVBF index was used to map the palaeochannels: it provides a flatness index between 0 and 8, with
scores of 8 being the flattest regions, which commonly includes
areas with the thickest regolith cover.

Results
The analytical and statistical tests, new detection limits and contamination filtering provided a robust dataset. The dataset generated in this study is available with the original report (Gray etal.
2014) or by contacting the authors.

Major geochemical parameters


Groundwaters of the northern Yilgarn are generally fresh, but
become more saline approaching palaeo-drainage channels/valley
floors, where water evaporates and salt lakes occur (Gray 2001).
However, there are a number of areas of saline fluids in upland
areas, which can be recognized when lowland groundwaters are
removed from the mapping (using MrVBF cut-off of 5.6; Slope
analysis section). Thus, in Figure 12 the highlighted areas denote
upland regions with anomalously high salinities. These areas are
generally associated with other anomalies:
A single sample at Area A (51000mg/L TDS; 1.5 x sea
water) is extremely saline for an uplands area. As expected,
it is at gypsum saturation, and additionally is anomalously
high in SO4, relative to Cl;
Area B (>5000mg/L) is an area which is anomalous in a
number of elements. It is potentially unrecognized greenstone assemblages under granite that is prospective for Au
and Ni (Gray etal. 2014);
Area F (>10000mg/L) sits along a granite greenstone contact. This is high in the landscape as it is the continental
watershed divide, and these salinities are highly anomalous.
Groundwater is generally neutral to weakly alkaline and oxidized
(Fig. 13). Although pH can be indicative of Fe sulphide weathering
at a local scale, these effects are not readily distinguished in the
regional dataset. In broad terms, granitic groundwater tends to be
weakly acidic to neutral, whereas groundwaters above greenstones
tend to be neutral to alkaline, a result of the increased abundance

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110

D.J. Gray etal.

Fig. 13. Groundwater pH and Eh


conditions in the northern Yilgarn Craton.
Grey areas are pH/Eh zones where Fe
is dominantly present as the relevant
solid phase. Created using Geochemists
Workbench, [25C, 1.013 bars, [Fe] =
0.001 M, [SO4] = 0.001 M, and [HCO3]
= 0.01 M, troilite (FeS) suppressed].
Modelling used the thermo.com.v8.r6+.
dat database, with additional data from
Warner etal. (1996).

of olivine and orthopyroxene in mafic and ultramafic rocks.


Relatively reduced groundwater (Eh below 260mV) is a response
to weathering of ultramafic rocks or nearby sources, such as
reduced palaeochannel sediments, rock sulphides, or even reduced
water sources from deep fault systems. Such effects have commonly been observed close to ore bodies and other sulphide systems, but are rarely observed in these regional shallow
groundwaters.

Lithological indicators
Several elements (particularly when combined as indices) are
effective lithological indicators. Note that this requires the element
in question to be generally soluble in these environments; thus rare
earth elements (elevated in granites for example) have little utility
in these fresh neutral groundwaters due to being commonly below
detection.
Gray (2003) demonstrated that dissolved Cr (as Cr6+) is a consistent indicator of greenstone lithology, particularly ultramafic
rocks at the prospect (<km) scale. This utility of dissolved Cr for
lithological mapping ultramafic rocks extends to the regional scale
(Fig. 14). At this sampling scale, most detectable dissolved Cr
occurs on or adjacent to greenstone belts, and is particularly related
to ultramafic rocks; commonly Cr concentrations >2g/L separate
greenstones from granites (the two major lithological groups in the
Yilgarn Craton). However, there are significant areas of high Cr in
the SE granite system surrounding the Leonora Leinster greenstones (Areas BE; Fig. 14). These are areas of deep weathering
and quite possibly significant transported cover, given the broad
drainage systems (>100km wide). These results suggest significant, unmapped or hidden, greenstone slivers within mapped
granite areas. In general, geological mapping of underlying lithology may be difficult where significant transported cover masks the
bedrock and inference of unit continuity linked with geophysics

contributes to large sections of the geological map. Future research


will move from the relatively exposed rocks of the northern
Yilgarn Craton to more covered terrains to test the potential of
these methods to map through cover.
The distribution of dissolved V also shows broad-scale variation spatially related to lithology (Gray etal. 2014), with greenstones having greater V concentrations than granites. Although the
spatial correlation with geology is not as close as for dissolved Cr
(Fig. 14), dissolved V is consistently >20g/L for groundwaters
contacting mafic lithologies. It also tends to be high in most of the
specific granite areas with anomalously high dissolved Cr. High
dissolved V in areas dominated by granite (particularly observed
in the west of the sampling area) may indicate V-rich granites,
potentially due to substitution in minerals such as magnetite (Dare
etal. 2014; Nadoll etal. 2014), biotite and muscovite (Tischendorf
etal. 2001, 2007), and tourmaline (Trumbull etal. 2008). The
availability of dissolved V from granites as well as mafic rocks
may be highly relevant to the location of secondary U (as carnotite;
K2(UO2)2(VO4)23H2O; Noble etal. 2011) as this represents additional sources for the V in this secondary mineral.
Whereas Cr and V occur in greater concentrations over greenstones compared to granites, the opposite is true for U. Uranium is
significantly higher in granites and is an additional lithological
indicator (Fig. 15). However, there are clear differences between
different granite areas: much of the SE granite area (12140'E/28S)
and, to a lesser degree, granites immediately east of Cue
(11810'E/2745'S) are low in dissolved U. Area F, with high dissolved U along the main NS drainage divide spine of the Yilgarn,
indicates a geochemical anomaly to the west of the Youanmi
greenstone/granite contact. Analogous variation in granite chemistry occurs with dissolved F (Gray etal. 2014).
Lithological discrimination can be improved by combining
element data. The Lithol1 index (V + Cr 2 U; Fig. 16)
more clearly separates greenstones (triangles; Lithol1 > 0.5) from

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Hydrogeochemistry of the northern Yilgarn Craton

111

Fig. 14. Groundwater Cr distribution for


the northern Yilgarn Craton.

Fig. 15. Groundwater U distribution for


the northern Yilgarn Craton.

Fig. 16. Lithol1 Index (V+Cr-2xU)


partially discriminates granites (dots) and
greenstones (triangles). Areas of granite
with significant Cr+V excess are circled.

granites (dots; Lithol1 < 0.3) than single element abundances.


Potentially, such indices could be used to map lithology in basinal
regions, such as east or north of the Yilgarn Craton margin. Similar
anomalous areas are observed in the Lithol1 index data as for single element results (e.g. Figs 14 and 15).
There is also potential to use ratios between major elements for
lithological discrimination. These parameters are expected to be
highly robust, as they use elements that are conservative in these
environments, and, if useful, will expand the utility of historical
groundwater data which commonly includes only major element
data. One useful parameter is Ca relative to Sr (Fig. 10): although
these elements are highly differentiated in rocks they have similar
reactivity in the regolith. Areas of high Ca:Sr are spatially correlated with greenstone belts (Fig. 17). As observed using the other
parameters discussed above, Ca-enrichment in the western part of
Area F is consistent with greenstone characteristics, although

anomalism is less apparent for Areas D, G and H. Rubidium related


to K (Fig. 18), also discriminates lithology, and does pick up Areas
B-E as all having mafic characteristics, although this index does
appear more noisy. For both indices, the values in Area J are
highly variable: this area to the NW is the older Narryer Domain
(Cassidy etal. 2006), which is highly altered and has been extensively structurally reworked, potentially leading to many lithological fragments. The K:Na index also partially discriminates
lithologies, but with more noise still.
This lithological discrimination can be recognized through statistical analysis. In Figure 19, overlays of the GLM statistical analysis (for the NE Yilgarn only) are presented on a map of the
regions geology. For the majority of sites the modelled geology
agrees with the mapped geology. Circles calculate as granites or
felsics, in agreement with geological mapping. Squares denote
groundwaters which calculate as granites or felsics, contrary to

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112

D.J. Gray etal.

Fig. 17. SrCaSW Index (see Fig. 10)


distribution in northern Yilgarn Craton
groundwaters.

Fig. 18. RbKSW Index distribution in


northern Yilgarn Craton groundwaters.

map. Triangles calculate as greenstones, in agreement with mapped


geology. Pentagons calculate as greenstone, though presently
mapped on this large scale geological map as granites/felsics.
Many of these, not surprisingly, occur near boundaries. However,
Areas B, C, E and I all show up as being spatially anomalous, with
the statistical analysis characterising samples within the areas as
greenstone groundwaters, though the geological mapping is as
granite. These are interpreted as unmapped rafts of greenstones,
or thin (<100m) layer of overburden of granitic material over other
rock types. These sites are strong candidates for new mineral
exploration.

Hydrothermal alteration indicators


Using some of the ion indices may help to identify the product of
hydrothermal processes such as addition of S or Mg-metasomatism.
The authors, and other researchers (de Caritat etal. 2005), have
previously observed that shallow groundwaters contacting NiS or
VHMS ore bodies are highly SO4 enriched (relative to assumed
conservative elements such as Cl or Br), due to oxidation of sulphide to sulphate. Use of this concept on a larger scale shows specific greenstone areas of excess SO4 (Fig. 20). Several of these
areas of excess S correlate with zones of marked K and Rb deficiency (Fig. 18) in the groundwater. Previous research in the
southern Yilgarn Craton (McArthur etal. 1989; Gray 2001) identified major K depletion in groundwaters related to precipitation of
alunite (commonly observed in the weathered zone within southern Australia; Bird etal. 1989; McArthur etal. 1989; Butt 2001;
Long etal. 2009) and/or jarosite:
K + + 3 ( Al3+ , Fe3+ ) + 2SO 4 2 + 6H 2O K ( Al, Fe )3 ( SO 4 )2 ( OH )6 + 6H +

( alunite/jarosite )

which requires excess SO4, and acidic conditions, such as commonly result from pyrite oxidation.
This study was very broad scale, and was generally 100s of
metres or more away from any known mineralization. However,
the mafic areas clearly have a high SO4:Cl ratio, with possible
higher SO4:Cl correlated with locations of faults (Fig. 20). Outside
mapped mafic rocks, Areas B-E all show moderate SO4:Cl enrichment; however this is also sporadically observed in other mapped
granite areas.
In addition, there are several point anomalies, possibly due to
specific sites, including Gidgee mine area (11920'E/27S), and
Windarra Well (12215'E/2830'S) a previous Ni mining area
with various prospects along strike.
Mapping areas of low dissolved Ba (Fig. 21) showed some similarity with the regional anomalies of SO4 and K, particularly with
regards to Area E. This is consistent with dissolved Ba being
removed in areas of high SO4 due to barite precipitation:
Ba 2+ + SO 4 2- BaSO 4

( barite )

These high SO4/low Ba waters could mix with surrounding


groundwaters, but might be expected to maintain the anomalously
low Ba character, albeit weakened by mixing. Note that these low
Ba groundwaters are all undersaturated with respect to Ba minerals
such as barite or witherite, so this effect is not directly from salinization or high pH.

Significance of groundwater anomalies


This large scale regional reconnaissance mapping has been done to
test the potential for mapping large scale systems, particularly

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Hydrogeochemistry of the northern Yilgarn Craton

113

Fig. 19. Lithological differentiation


from GLM analyses of groundwater
geochemistry (using Rb, Cr, U, B, Ca, Cl,
Sr, Ba, F, Mg, Co, HCO3, Br, V, Na) for
NE Yilgarn Craton.

Fig. 20. SO4ClSW Index distribution in


northern Yilgarn Craton groundwaters.

Fig. 21. Dissolved Ba in northern Yilgarn


Craton groundwaters.

under cover. This study demonstrates the validity of this technique,


and here we also identified several areas of significant anomalism.
In particular, Areas BE and, to a lesser degree, HK indicate
rafts of prospective greenstone slivers or altered granites unrecognized previously because they mainly occur in highly weathered
terrains with playas and exotic cover. Analysis of the broad scale
gravity geophysical measurements indicates Area B to have denser
rocks, supporting the hypothesis of incorrect lithological assignment. In Areas A, D, H and G there is little indication of higher
density rocks in the regional gravity, possibly due to insufficient
data density and/or obscuring of the gravity measurements by
thick overburden.

Groundwater results from this study encouraged exploration in


Area F by Resource Mining Corporation Ltd (RMC), who observed
komatiitic rocks in drill spoil (RMC 2010), validating the groundwater-based interpretation.

Conclusions
In contrast to southern regions of the Yilgarn Craton (Gray 2001),
the waters in the northern Yilgarn Craton are fairly homogeneous
and dominantly fresh and neutral, though with increased groundwater salinity in the base of palaeo-drainages and close to
salt lakes. The groundwaters also have relatively low dissolved

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114

D.J. Gray etal.

concentrations of metals compared with groundwater from the


southern Yilgarn. Understanding of water chemistry, along with
new approaches to measurement and filtering for contamination
has allowed the development of a number of interpretative outputs.
These outputs include:
Metrics for contamination, and statistical analysis of elemental sensitivity to contamination, providing greater confidence in the data.
Lithological indicators (Cr, V, U and other elements,
Lithol1 index, Sr:Ca, Rb:K etc.), separating greenstones
from granites and mapping lithology through cover at the
sample spacing of 4-10 km used in this study.
Identification of previously unrecognized zones for potential mineral occurrences where interpretations from
groundwater differ from previous geological mapping.
Areas of S enrichment that are related to varying geological areas and/or fault structures, the latter indicating that
these structures still have active input into the surface environment.
Anion excess and depletion methods have been developed
and are a valuable for detecting sulphides. This coupled
with multi-element indices (Gray etal. 2014) provides a
solid platform for the use of hydrogeochemistry in exploration for sulphide occurrences in relatively fresh and neutral
groundwater environments.
Groundwater chemistry determined from samples collected from
bores and wells is useful for defining lithological changes, hydrothermal alteration and mineralization. The developed methods and
interpretation from this study of more than one thousand waters
sampled from the shallow aquifer of the northern Yilgarn Craton
can be applied to extend exploration into other covered areas with
similar groundwater characteristics. Similar groundwater environments include much of the northern two thirds of Australia, particularly the underexplored basins and Craton margins. Provided
that access to groundwater exists, hydrogeochemical exploration
provides a tool to evaluate prospectivity and improve exploration
efficiency in areas of cover and difficult terrain.Acknowledgements
and Funding

Acknowledgements and Funding


This project was supported by CSIRO, GSWA and by MERIWA (Projects M402
and M414) and the specific industry sponsors. Richard Jarrett provided extensive advice in the development of generalized linear models for lithological
discrimination.
Financial support was provided by the following industry sponsors: Agnew/
Goldfields, AMF, Anglo-American, AngloGold Ashanti, Aragon Resources,
Areva, Resources, Avoca Resources, Barrick, BHP-Billiton, Cameco, Crescent
Gold L, Cullen Resources, Drake Resources/Aura Energy, Echo, Encounter
Resources, Enterprise Metals, Geotech, Heron Resources, Image Resources/
Emu Nickel, Independence Group, Jindalee Resources, Maximus Resources,
Mega Redport, Mindax, Minjar Gold, New Era, Newmont, Norilsk, Oz Minerals,
Regalpoint, Rio Tinto Exploration, RMC, Spark Energy, Thundelarra, Toro
Energy (Nova Energy), Troy Resources, Venture Minerals, Venus Resources,
Windy Knob Resources. Further in-kind and financial support from MERIWA,
Geological Survey of Western Australia, Geoscience Australia, CRC LEME,
DET CRC, and Department of Water made this project possible.
Additional, in-kind support for accommodation was provided by Apex
Minerals, Darlot Mine site (Barrick), Echo Resources, BHPB and Troy
Resources.

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