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Geochemistry Exploration, Environment, Analysis 2016 Gray 100 15
Geochemistry Exploration, Environment, Analysis 2016 Gray 100 15
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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
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
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
101
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.
102
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
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
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).
104
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.
105
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
, log10
, log10
, log10
CV = Mean log10
, log10
0.277
6.94
0.234
0.059
0.546
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%
106
107
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.
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
108
109
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).
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
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.
110
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
111
112
( 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 )
113
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
114
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