Ground Water Carbon

MDU Flagship Exploration and Technology Guide
FIELD GUIDE FOR MINERAL

EXPLORATION USING
HYDROGEOCHEMICAL ANALYSIS
David Gray, Ryan Noble and Alan Gill
CRCLEME
Cooperative Research Centre for

L andscape E nvironments
and M ineral E xploration
© This report is the copyright of the Commonwealth Scientific and Industrial Research Organisation (CSIRO).
Apart from any fair dealing for the purpose of private study, research, criticism or review, as permitted
under Copyright Act, no part may be reproduced or reused by any process whatsoever, without prior
written approval from CSIRO.
Reference:
Noble, R.R.P., Gray, D.J. & Gill, A.J. 2011. Field guide for mineral exploration using hydrogeochemical analysis.
1. Mineral exploration 2. Geochemistry 3. Groundwater
Epublish Report Number: EP113936
ISBN: 9780643107182
Publisher: CSIRO Earth Science and Resource Engineering, PO Box 1130, Bentley, WA 6102
Editor: Alan Gill
Copy editors: David Gray, Ryan Noble and Indra Tomic
Series editor: Ryan Noble
Transmogrify and design: Travis Naughton and Angelo Vartesi, CSIRO Creative Services Western Australia.
Correspondence:
David Gray
CSIRO Earth Science and Resource Engineering
Australian Resources Research Centre
26 Dick Perry Avenue
Kensington WA 6151
david.gray@csiro.au
Disclaimer: The user accepts all risks and responsibility for losses, damages, costs and other consequences
resulting directly or indirectly from using any information or material contained in this report. To the
maximum permitted by law, CSIRO excludes all liability to any person arising directly or indirectly from
using any information or material contained in this report.
Hydrogeochemical analysis: Field Guide i

ii Hydrogeochemical analysis: Field Guide
CONTENTS
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Field guide purpose . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Location and physical setting . . . . . . . . . . . . . . . . . . . . . . 2
1.3 Exploration targets . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Overview: Mineral exploration using hydrogeochemical analysis . . . 3

2.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2 Limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3 Benefits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Groundwater sources . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1 Windmills and wells . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2 Bores/drill holes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4. Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.1 Water collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.2 Sample storage and filtration . . . . . . . . . . . . . . . . . . . . . . 7
4.3 Field measurement equipment . . . . . . . . . . . . . . . . . . . . . 10
4.4 Field measurement chemicals . . . . . . . . . . . . . . . . . . . . . 10
4.5 Carbon sachets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5. Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5.1 Planning the study . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5.2 Site investigation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5.3 Prepare equipment and filtration unit . . . . . . . . . . . . . . . . . 13
5.4 Prepare and label bottles . . . . . . . . . . . . . . . . . . . . . . . . 14
5.5 Sample groundwater . . . . . . . . . . . . . . . . . . . . . . . . . . 14
5.6 Chemical analysis in the field . . . . . . . . . . . . . . . . . . . . . . 14
5.7 Filtered sample collection . . . . . . . . . . . . . . . . . . . . . . . 15
5.8 Unfiltered sample collection . . . . . . . . . . . . . . . . . . . . . . 15
6. Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
6.1 Anion analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
6.2 Alkalinity analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Hydrogeochemical analysis: Field Guide iii

6.3 Cation analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
6.4 Gold/Platinum group elements analysis . . . . . . . . . . . . . . . . 19
6.5 Mapping and interpreting results . . . . . . . . . . . . . . . . . . . . 19
7. Case Study 1: Harmony gold deposit . . . . . . . . . . . . . . . . 21

7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
7.2 Location . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
7.3 Regolith characteristics . . . . . . . . . . . . . . . . . . . . . . . . . 21
7.4 Groundwater depth and chemistry . . . . . . . . . . . . . . . . . . 22
7.5 Sample results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
7.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
8. Case study 2: Groundwater Uranium from farm wells and bores . . 25

8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
8.2 Location . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
8.5 Sample results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
8.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
9. Case Study 3: Groundwater for nickel sulfide exploration . . . . . . 31

9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
9.2 Location . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
9.5 Sample results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
9.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
10. Quick reference guides . . . . . . . . . . . . . . . . . . . . . . . 37

10.1 Standard Abbreviations For Sampling . . . . . . . . . . . . . . . . . 37
10.2 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
10.3 General sampling and testing methods flowchart . . . . . . . . . . 38
iv Hydrogeochemical analysis: Field Guide

11. Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . 39
12. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
13. Glossary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
13.1 Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
13.2 Elements/Compounds . . . . . . . . . . . . . . . . . . . . . . . . 46
13.3 Units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
Hydrogeochemical analysis: Field Guide v

vi Hydrogeochemical analysis: Field Guide
1. INTRODUCTION
1.1 Field guide purpose
This Field Guide is designed to assist exploration geologists in using
hydrogeochemistry for mineral exploration. Primarily presenting the work of
Dr David Gray, Dr Ryan Noble and others from CSIRO’s Minerals Down
Under National Research Flagship, this Guide outlines the materials, methods
and analytical techniques to enable any exploration geologist to use this
method. Case studies are presented to give an example of how this exploration
method can be applied.
> Figure 1: Groundwater salinity in Australia (from Jacobson and Lau, 1987)
Hydrogeochemical analysis: Field Guide 1

1.2 Location and physical setting
Groundwater exists across most of Australia, making this method applicable in
almost every region. Due to changes in groundwater salinity, this method can
become less effective due to analytical limitations. Most of the southern fifth of
Australia, for example, has groundwater reserves that are highly saline, reducing
the sensitivity of this method for elements present in low concentrations.
Figure 1 gives an approximate overview of groundwater salinity in Australia.
1.3 Exploration targets

Different minerals react with groundwater in different ways, resulting in
different elements becoming present within groundwater samples. Table 1
provides an indication of what ore groups can be indicated by their associated
elements in hydrogeochemical analysis, however groundwater conditions may
not contain all these elements in a soluble and detectable phase.
Ore group Associated elements

Magmatic Ni, Cu, Co, PGE, Te, As
Metasomatic Cr, PGE, Ni, Cu, Co, Au, Fe, Ti, V
Hydrothermal epigenetic Sn, W, As, Cu, Zn, W, Mo, Pb, Bi, Te,
Nb, Li, Be, Cs, Rb, U, Au, Re, Ag, Hg,
Se, Pt, Pd
Exhalative diagenetic Cu, Zn, Pb, As, Sb, Bi, Sn, Mo, Se, Ag,
Au, Ba, Hg, Te, Co, Cd, Mn, In, Ni
Marine sedimentary Fe, Mg, Al, Ca, Mn, P, Ti, Mn, Zn, Li, Ba
Residual & supergene Al, Fe, Ti, Nb, Ga, Mn, Zn, Zr, Ni, Co,
Cr, Au, Ag, As, W, Sb, Bi, Sr, Ca, K, U,
Ta, V, Se, Mo, Cu, Pb
Placers Au, Ag, W, Ti, Zr, Ba, Fe, Zr, Th, Cr, Sn,
Nb, Ta
> Table 1: Ore groups with associated elements to assist in mineral targeting (adapted
from Butt et al. 2005 p2)
2 Hydrogeochemical analysis: Field Guide

2. OVERVIEW: MINERAL EXPLORATION USING
HYDROGEOCHEMICAL ANALYSIS
2.1 Background
The use of hydrogeochemistry for mineral exploration is increasing
worldwide. Within Australia, extensive research was conducted by the
Cooperative Research Centre for Landscape Environments and Mineral
Exploration (CRC LEME) (Noble & Gray 2010; Gray 2001; de Caritat & Kirste
2005). Internationally, examples of this technique can be found in India (de
Caritat et al. 2009), Canada (Maclean et al. 2000; Cameron, 1978), U.S.A.
(Langmuir & Chantham 1980), Chile (Leybourne & Cameron 2006) and
Russia (Goleva 1979).
This exploration method exploits the interaction between groundwater
systems and geology. Research has shown that in known areas of
mineralisation, chemical traces can be found within groundwater samples. By
examining groundwater samples across an area of interest, concentrations in
pathfinder minerals should indicate where mineralisation most likely occurs.
From the inferences gathered by this exploration technique, traditional
exploration methods should be used to confirm the location and economic
viability of discovered deposits.
2.2 Limitations
In some parts of Australia, groundwater can be saline.This can present an issue
as salts require the samples to be appropriately diluted before analysis, which
lowers the concentration of elements that are being detected. Generally,
in the case of cation analysis, dilution is needed if the total dissolved solids
(salt content) exceeds 0.2 per cent. Dilution may result in trace (pathfinder)
element concentrations dropping below analytical detection limits.
2.3 Benefits
By using groundwater analysis, mineral exploration can be completed faster
and cheaper than by traditional techniques alone. Sample density is lower and
if agricultural infrastructure (e.g. windmills, bores) is available, few, if any, bore
holes will need to be drilled.

3. GROUNDWATER SOURCES
Sources of groundwater must be considered when planning a hydrogeochemical
exploration program. Each type is subject to its own set of limitations, therefore
comparisons during analysis must be made between similar sample sites.
Table 2 shows the advantages and disadvantages of various groundwater
sources while a summary is provided overleaf.
Groundwater Advantages Disadvantages

source
Windmill Easy access; Potential for contamination if not
no drilling costs regularly flowing; restricted
available sample sites; only
shallow groundwater
Open well Easy access; Potential for contamination if not
no drilling costs regularly flowing; restricted
available sample sites; shallow
groundwater only
Water bore Easy access; Uncommon;
contamination mainly shallow groundwater
unlikely
RC or RAB Commonly Potential for contamination;
drill hole available in the often not cased and may close or
exploration area collapse shortly after drilling
of interest
Diamond core Commonly Commonly deep groundwater;
drill holes available in the generally cased to a significant
exploration area of depth preventing sampling from
interest; well cased shallow groundwater systems
and preserved
Monitoring Easy access; Uncommon; shallow
bore contamination groundwater only
unlikely
> Table 2: Groundwater sources with advantages and disadvantages of each (modified
from Noble & Gray 2010)

3.1 Windmills and wells
Established windmills and wells provide easy access to groundwater without
the cost of drilling bores. However, in most regions (exceptions being areas
such as Great Artesian Basin bores) these access points only allow testing
of shallow groundwater systems and may be contaminated if they are not
regularly flowing (Noble & Gray 2010).
3.2 Bores/drill holes

Where windmills and wells do not exist, it is necessary to utilise an existing
bore hole or drill a new one. When choosing which bores to use, consideration
must be made as to the depth of the system it is drawing water from. Samples
should be compared with those drawn from a similar depth; otherwise it is
possible that different groundwater systems could be sampled which may not
share similar chemical properties.

4. MATERIALS
In order to successfully complete an exploration program, appropriate
equipment is required. This section details what is needed to collect and store
samples, as well as equipment to conduct analysis in the field and chemicals to
prepare samples for laboratory analysis.
4.1 Water collection

Groundwater samples can be retrieved either by using the output from a
windmill or bailing water from a bore hole. A summary of advantages and
disadvantages is shown in Table 3.
Collection Advantages Disadvantages

method
Direct sampling Quick; only a bucket Potential contamination,
from windmill is needed restricted sites
Bailing from bore Quick; portable Potential contamination
hole
> Table 3: Collection method with advantages and disadvantages (modified from
Noble & Gray 2010)
If direct sampling from a windmill is used, all that is required to collect the
sample is a plastic bucket.
When a bore is used, disposable plastic bailers are effective. If cleaned properly
and still in good condition, they can be reused. Heavier steel bailers should be
used when an angled drill hole is the access point to groundwater. If a depth
marker is not on the bailer retrieval cord, depth marking should be made
with a depth probe to ascertain the depth of the water table. Examples of
bailers are shown in Figure 2.
4.2 Sample storage and filtration

New and clean HDPE plastic bottles are ideal for sample storage as they
are chemically stable and unlikely to contaminate samples (Reimann et al.
1999). However, contamination risk should be monitored by way of testing
control bottles (Reimann et al. 2007). CSIRO use two bottle sizes: 125 mL for
> Figure 2: Disposable and stainless steel/polycarbonate bailers on retrieval cords
anion, cation and alkalinity test samples and 1000 mL for Au/PGE test samples.
Examples of suitable storage bottles are shown in Figure 3.
To avoid contamination by sediment and organic material, groundwater
should be filtered immediately after retrieval before being stored or tested.
Filtration units such as Nalgene® with a maximum filter paper pore size of
0.45 µm are ideal.These units require a pump to ensure filtration time is short.
Alternatively, syringe filters can be used when small samples (< 50 mL) are
required, though care should be taken to choose syringes with all-plastic parts
rather than rubber to reduce the risk of contamination. Examples of filtration
equipment is shown in Figure 4.
Samples should be stored in a cool place out of direct sunlight.

> Figure 3: Storage bottles
> Figure 4: Filtration equipment

4.3 Field measurement equipment
Although the samples collected are to be tested at a later stage, pH, electrical
conductivity (EC), redox potential (Eh) and temperature should be measured
in the field. This is done to achieve the most accurate values possible, as pH,
Eh and temperature are likely to change soon after the sample is collected and
exposed to air. To do this, the following equipment is needed:
• Thermometer (often part of the pH or conductivity electrode)
• pH meter and electrode
• Conductivity meter and electrode
• Oxidation/Reduction Potential (ORP) meter and electrode
When choosing equipment it is important to consider the sensitivity required
and units measured. For example, highly saline groundwater in parts of
southern Australia means that EC meters should measure up to 200 mS/
cm while other regions may only require an EC meter with a maximum
measurement of 2000 µS/cm.
4.4 Field measurement chemicals

Chemicals are required to calibrate field measurement equipment and
prepare samples to take back to the laboratory.
Calibration solutions for the pH and EC meters are required and should be
used daily. The Eh meter should be calibrated fortnightly or after a field trip.
Depending on the type of electrodes used in each meter, a saturated solution
of KCl may be useful in storage. Deionised (DI) water is also required to rinse
electrodes. and other equipment
While most samples that will undergo later analysis can be prepared in the
laboratory, it is ideal, and straightforward, to prepare the Au/PGE sample on
site. For this, approximately 10 g of solid NaCl (1 Tbs) and carbon sachets are
required.

4.5 Carbon sachets
Activated carbon sachets are used to absorb and concentrate Au, Ag and PGE
to allow low-level detection in the order of ng/L.
Carbon sachets are made by heat sealing a nylon mesh casing filled with 1 g
of activated carbon. The casing dimensions should be approximately 2 cm x
4.5 cm. The carbon sachet is shown in Figure 5.
1 cm
> Figure 5: Carbon sachet

5. METHODS
5.1 Planning the study
While hydrogeochemical analysis has the potential to target some commodities
with sample spacing up to 5 km, greater sample density is preferable. When
planning an exploration study it is important to identify where samples will
be obtained, what sources will be used and how much drilling is needed, if
necessary. By plotting locations of known wells, bores and windmills, gaps in
sample coverage will emerge. Consultation with various maps (e.g. cadastral,
geological and hydrological maps) will help identify what sites would be
suitable for bore drilling. From this a list of sample sites and sampling schedule
can be created.
Ideally two people should carry out the field work, with one person collecting
the samples while the other performs the “clean” work of filtering, sample
preparation and measurements.
5.2 Site investigation

Before samples are collected, observations of the sample site should be taken.
These should include:
• location (latitude and longitude or AMG coordinates etc)
• vegetation cover
• type of sample source (e.g. bore, windmill etc.)
• condition of source (e.g. Is it regularly used? Is it cased? If so, what
condition is the casing in and what is it made of?)
• potential sources of contamination.
It is important to note these and any other observations so that samples can
be compared with those obtained from similar sources (Quick Reference
Guide 10.1).
5.3 Prepare equipment and filtration unit

Bailers or other water collection equipment should be rinsed with DI water
prior to the collection of each sample, as should the filtration equipment. For

each sample, use a new filter paper or syringe filter and ensure it is free from
contamination.
5.4 Prepare and label bottles

Label the following sized bottles with a site identification number and type of
future analysis on the cap, shoulder and body of the bottle.
Bottles required are:
• bottle #1: anion analysis (125 mL)
• bottle #2: alkalinity analysis (125 mL)
• bottle #3: cation analysis (125 mL)
• bottle #4: Au/PGE analysis (1 L)
5.5 Sample groundwater

If collecting samples from a bore hole, lower the bailer until the sampler feels
(or hears) the water table. Make a note of the depth. Continue to lower the
bailer until the desired sampling depth is reached. To reduce the chance of
oxidation, a sampling depth of at least 5 m is ideal (Gray & Noble 2006a; Giblin
2001) (Quick Reference Guide 10.2).
The first sample retrieved is used to rinse the bailer and the measurement
electrodes. Discard and repeat the bailing procedure until approximately 2 L
of water is collected.
5.6 Chemical analysis in the field

Place the initial bailer rinse-water into a container with the electrodes
on and start the devices, but do not record the results. Empty the bailer.
The second sample of water is used in the container to measure water
parameters. Record Eh, pH, EC and temperature over 5-15 minutes until
the readings stabilise. In some cases Eh may still vary up to 50 mV. Ideally,
Eh measurements should be made in a flow-through cell to avoid the
introduction of air into the sample that can cause erroneous measurements.
For exploration purposes this is not often practical so it is important to
measure the water quickly after it is retrieved and not to let the water stand
for more than 15 minutes. Reduced groundwater (<200 mV) readings may

decrease and then begin to rise. If this occurs, record the lowest reading
as this is the most relevant for later processing. For EC and pH, the most
stable measurements are used. It is good practise, however, to record all
measurements over time.
5.7 Filtered sample collection

Initially filter a sample of approximately 100 mL. After all the water has passed
through the filter membrane, do a single rinse into bottle #1 (anion analysis)
by pouring approximately 5 mL into the bottle, capping and shaking, then
discarding the water. Pour the rest of the filtrate into the bottle.
Filter another 150 mL of water. Rinse twice, in the same manner as above.
Discard. Fill bottle #3 with the remaining filtrate. This can be acidified in the
field or laboratory with nitric acid to a concentration of 0.2% v/v or 250 µL of
concentrated acid in 125 mL of sample.
5.8 Unfiltered sample collection

Fill bottle #2 (alkalinity analysis) with sample water so that it is completely full,
taking care to ensure there are no air bubbles or space at the top.This is done
to prevent reaction with the air.
Fill bottle #4 (Au/PGE analysis) to within 2 cm of the top of the bottle.
Add the carbon sachet to the bottle, along with 10 g (1 Tbs) of NaCl. For
simplicity and reduced contamination in the field the carbon and salt can be
pre-added to the bottles.

6. ANALYSIS
6.1 Anion analysis
Bottle #1 is used for major anion, dissolved organic carbon (DOC) and PO4
analysis.
Ion Chromatography (IC) is used to detect major anions such as Br, Cl, F,
NO3 and SO4. Commercial laboratories routinely conduct this analysis.
Environmental analytical laboratories will be more familiar with these methods
than mining-type laboratories.
DOC should be analysed using a dedicated DOC analyser while PO4
concentration can be established using titration.
Element/ Method Detection limit Units

Compound
Br IC 0.1 mg/L
Cl IC 10 mg/L
DOC DOC analyser 0.2 mg/L
F IC 0.01 mg/L
NO3 IC 1 mg/L
PO4 Titration 0.009 mg/L
SO4 IC 3.5 mg/L
> Table 4: Typical detection limits for anions
6.2 Alkalinity analysis

Bottle #2 is used to establish concentration of HCO3. A set volume (e.g.
25 mL) of the sample should be titrated against a known concentration of acid
(e.g. 0.01 M HCl) to an end point pH of 4.3. This can be conducted in the
field using a burette, stirrer and pH meter, though it is rather time consuming.
Commercial laboratories are capable of conducting this test. It is preferable to
have the sample tested as soon as possible.
This method has a detection limit of approximately 2 mg/L.

6.3 Cation analysis
Bottle #3 is used for major, minor and trace metal analysis using Inductively
Coupled Plasma Mass Spectrometry (ICP-MS) and ICP-Optical Emission
Spectrometry (ICP-OES).
Element/ Method Detection limit Units

Compound
Al ICP-OES 0.002 mg/L
As ICP-MS 0.01 µg/L
B ICP-OES 0.1 mg/L
Ba ICP-MS 0.01 µg/L
Ca ICP-OES 0.1 mg/L
Cd ICP-MS 0.01 µg/L
Ce ICP-MS 0.01 µg/L
Co ICP-MS 0.01 µg/L
Cr ICP-MS 0.01 µg/L
Cu ICP-MS 0.01 µg/L
Fe ICP-OES 0.004 mg/L
Ga ICP-MS 0.01 µg/L
K ICP-OES 0.08 mg/L
La ICP-MS 0.01 µg/L
Li ICP-OES 0.01 mg/L
Mg ICP-OES 0.04 mg/L
Mn ICP-OES 0.05 mg/L
Mo ICP-MS 0.01 µg/L
Na ICP-OES 0.006 mg/L
Nd ICP-MS 0.01 µg/L
Ni ICP-MS 0.01 µg/L
Pb ICP-MS 0.01 µg/L
Rb ICP-MS 0.01 µg/L
Sb ICP-MS 0.01 µg/L
Si ICP-OES 0.5 mg/L
Sn ICP-MS 0.01 µg/L
Sr ICP-OES 0.008 mg/L
U ICP-MS 0.01 µg/L
> Table 5: Typical detection limits for cations

To prevent Fe precipitates this sample is acidified using high purity nitric acid
to a concentration of 0.2% v/v. If orange precipitates are still present a day
after acidification, continue to add acid incrementally over the next few days
until the precipitate is dissolved. Commercial laboratories can conduct this
preparation step.
ICP-MS and ICP-OES can be conducted by most commercial laboratories.
6.4 Gold/Platinum group elements analysis

Bottle #4 is used to detect Au, Pt, Pd and Ag. The carbon sachet inserted into
the 1000 mL bottle should be left for at least 4 days and the bottles should
ideally be placed on a shaker or roller.The carbon sachet is removed and dried,
and the volume of water collected is determined at this stage. Prior to
measurement using ICP-MS the sachet is prepared by ashing the nylon mesh
and C, followed by dissolution in aqua regia.
This process can be conducted by specialised commercial laboratories.
Element/ Method Detection Units

Compound limit
Ag ICP-MS Carbon 20 ng/L
Au ICP-MS Carbon 2 ng/L
Bi ICP-MS Carbon 5 ng/L
Pd ICP-MS Carbon 3 ng/L
Pt ICP-MS Carbon 2 ng/L
> Table 6: Detection limits for Au/PGE in activated carbon
6.5 Mapping and interpreting results

To identify areas of higher concentration of the target mineral, it is useful to
overlay concentrations of relevant elements from each sample site on a map.
An example of this is shown in Figure 6.
Element mapping alone won’t always suggest areas of mineralisation. It is often
necessary to look at an aggregate of elements or whether the groundwater is
near saturation point for a particular mineral. This is known as the saturation
index (SI).

6.6 Saturation Index
Saturation indices for each water sample for different minerals can be calculated
using various computer programs, such as PHREEQE (Parkhurst et al. 1980),
many of which are available online. If the SI for a mineral equals zero, the water
is in equilibrium with that mineral. If SI is less than zero, groundwater is under-
saturated, suggesting that if minerals are present they are likely to dissolve. If
SI is greater than zero, the groundwater is over-saturated with respect to that
mineral, suggesting that mineral precipitation may occur.
C Au Mines
! Ag (ng/L)
26°S
2700 - 8200
700 - 2290
450 - 680
C
! 250 - 428
C
! 150 - 223
C
!
C
! 100 - 120
50 - 73
27°S
C
! < 50
C
!
C
!
C
!
C
! C
!
28°S !
C
C
!
C
!
C !
C!
! C
C
!
29°S
100 km C
!
118°E 119°E 120°E 121°E 122°E
Figure 6: Example of mapping concentrations from sample sites. This image shows Ag
concentrations in the northeast Yilgarn Craton (Gray et al. 2009).

7. CASE STUDY 1: HARMONY GOLD DEPOSIT
Source: Noble et al. 2010
7.1 Introduction
This case study examined which elements are useful pathfinders to locate gold,
utilising known deposits on the northern Yilgarn Craton in Western Australia.
7.2 Location
The Harmony Au deposit is located within a depositional plain approximately
90 km north of Meekatharra in the mid west region of Western Australia.
The region is arid, with low, irregular rainfall averaging 240 mm per annum
(Bureau of Meteorology, 2008).The sparse vegetation consists largely of mulga
(Acacia aneura), and drought-resistant shrubs and grasses. The deposit was
discovered in 1991 by RAB drilling to saprolite and fresh rock.
7.3 Regolith characteristics

The site is located in the Palaeoproterozoic Bryah Basin. The mineralisation
is on the contact between the Ravelstone and Narracoota Formation. The
Ravelstone Formation is a thick turbidite sequence of fine-grained, mafic,
feldspathic and lithic wackes. The Narracoota Formation consists of folded
mafic and ultramafic volcanics. The sequences are metamorphosed to lower
to middle greenschist facies (Pirajno & Occhipinti 1995; Pirajno et al. 1995).
Primary mineralisation is associated with hematitic quartz veins and carbonate-
filled breccia, with Au and Ag occurring as inclusions in pyrite with associated
pyrrhotite, pentlandite, chalcopyrite and scheelite. Trace element signatures
in the mineralised rocks include As, Te, Zn and Pb, with Au and W the most
useful pathfinders (Harper et al. 1998).
The deposit has been weathered to ferruginous saprolite and covered by
colluvium-alluvium. Colluvium-alluvium in the area is 7-12 m thick, but directly
over the deposit (a palaeo-high) it is 1-3 m thick. The upper few metres
of the colluvium-alluvium are silicified to a red-brown hardpan. Below this,
the material is similar, but finer grained and uncemented. Adjacent to the
deposit, but beneath the colluvium-alluvium, the deposit is flanked by a lateritic
duricrust of approximately 8 m thickness. A palaeochannel drains from 1 km

south of the deposit in a northwest direction (Figure 7). The palaeochannel
is filled with 10-24 m of mottled, thick, puggy, clay-rich sediments (Robertson
2001).
118°37'50" E 118°37'50" E
Au in water (µg/L) Mo in water (µg/L)
0.007 - 0.011 4-9
0.005 - 0.006 250 m 2-4 250 m
0.003 - 0.004 0.3 - 2
0.002 - 0.003 < 0.2
25°39'10" S 25°39'10" S
Palaeochannel Groundwater flow direction

Au in Regolith (µg/kg) > 3200 1600 - 3200 400 - 1600 100 - 400 < 100
> Figure 7: Dissolved Au and Mo concentrations in groundwater superimposed over

maximum Au concentrations in regolith. Mining pit outlined towards the centre;
paleochannel and groundwater flow direction also shown.
7.4 Groundwater depth and chemistry

The shallow aquifer < 2 km from the deposit has a neutral pH, is fresh and
generally similar to those from the northern Yilgarn Craton. The groundwater
flows southeast, towards the channel.
7.5 Sample results

Approximately 40 samples were collected from drill holes over a 6 km2 area.
Dissolved Au concentrations are low (2-11 ng/L) and ~100 times less than
in mineralised areas around Kalgoorlie. Despite these low concentrations,

dissolved Au is a good target element for mineralisation in the region, as local
background is lower still.
Some groundwater has concentrations of Au below detection over
mineralisation that may indicate inconsistencies in Au mobility in this
environment. Additionally, Sc, Mo, W and possibly Rb have elevated
groundwater concentrations in areas of Au mineralisation and are more
consistent pathfinders than Au itself in groundwater at this local scale. This
elemental suite is similar, though more limited, to those observed elsewhere in
the northern Yilgarn for detecting Au mineralisation. Dissolved As correlated
with the areas of major hydrothermal alteration.
7.6 Conclusion
Through sampling groundwater from 40 bore holes near the Harmony Au
deposit, Au, Mo, W and Rb concentrations in groundwater corresponded to
known concentrations of Au in the regolith.

8. CASE STUDY 2: GROUNDWATER URANIUM
FROM FARM WELLS AND BORES
Source: Noble et al. 2011
8.1 Introduction
Hydrogeochemistry has been demonstrated to be a useful tool in mineral
exploration, though its efficacy over a multi-catchment area is much less
known. This case study examines the application of this exploration method
at a regional scale, while also examining the role of the saturation index (SI) in
targeting known U deposits.
8.2 Location
The northern Yilgarn region is semi-arid to arid with hot, dry summers and
cool winters, with low, irregular rainfall between 200-300 mm per annum
(Bureau of Meteorology, 2010).The sparse vegetation consists largely of mulga
(Acacia aneura), and drought-resistant shrubs and grasses. Halophytic shrubs
Drainage divide Regional

Groundwater
26°S Samples
Playas
Towns
Meekatharra Wiluna Study area
Drainage divide
Catchment
27°S boundaries
Cue
Leinster
Sandstone
28°S
Mt Magnet
Laverton
Leonora
29°S
100 km
118°E 119°E 120°E 121°E 122°E 123°E
> Figure 8: Northern Yilgarn Craton study area showing towns, water catchments, playas
and sample locations

are located on the fringe of the playas. The study area, including towns, water
catchments, playas and sample locations is shown in Figure 8. The northern
Yilgarn is separated from the south by the Menzies Line, a distinct ecological
divide between 29º to 30º S latitude (Anand and Butt, 2010) where soil type,
groundwater and vegetation change over a relatively short distance (~50 km;
Butt et al., 1977). Generalised and distinctive differences in conditions between
the north and south Yilgarn are well known and are influential in U deposit
formation, but the evolution of these conditions has only recently been
investigated (Gray and Noble, 2006b; Peiffer et al., 2009).

The northern Yilgarn Craton consists of Archaean granite and granitic
gneiss with extensive north-north west oriented, elongate greenstone belts
(Myers, 1997; Williams, 1975). The granitic rocks comprise deformed and
metamorphosed granodiorite-monzogranite. The greenstones generally
comprise mafic and ultramafic volcanic rocks underlain by quartzite, banded
iron formation and minor felsic volcanics. A summary of the tectonic evolution
of the Yilgarn Craton is given by Cassidy et al. (2006).
The topography is broadly flat with Cainozoic alluvial transported cover of
varied thickness (a few metres to tens of metres). Elevation across the sampling
area ranges from 360 to 600 m above sea level, gradually decreasing north
to south and is split by a north-south trending drainage divide (Figure 8).
The relatively flat surface hides complex underlying regolith that has been
exposed to significant events of weathering, erosion, deposition and a
variety of climatic conditions. A comprehensive review of the regolith and
geomorphology of the region is given by Anand and Paine (2002). Major
complexity in composition and ages of the weathered surface occurs in the
northern Yilgarn. The dominant residual regolith on uplands is characterised
by saprock, grading upwards to saprolite that is commonly bleached. Overlying
this are clay- and quartz-rich, mottled- and ferruginous zones (lateritic
residuum) near the surface. The channels are weathered surfaces that have
been filled with clays, sand and silt with lenses of carbonates, lignites and
ferruginous gravel (Anand and Paine, 2002). Carbonates are formed primarily
in the upper part of the channel. Generalised cross sections of these two

dominant landform features are shown in Figure 9. Other common landforms
of the northern Yilgarn Craton are sand plains, plateaus, breakaways, colluvial
and alluvial plains, minor bedrock exposure, playas and sand dunes. Soils are
dominantly acidic, sandy with red-brown hardpans and lack significant calcrete
horizons except in channels.

Regionally, the groundwater is relatively fresh and of neutral pH (Gray, 2001).
Salinity tends to increase towards the drainages and valley floors where, in
many cases, there are playas (with a salt crust). The water table is commonly
5 to 40 m below the surface, with the shallowest depth to groundwater
occurring in the valley floors.
Oxidized groundwater (Eh >260 mV) is common in the northern Yilgarn
shallow aquifers, however reduced groundwater (Eh <260 mV) has been
observed and related to nearby sources, such as reduced palaeodrainage
sediments, rock sulphides, or even reduced water sources from deeper fault
systems (Gray 2001; Gray and Noble, 2006a).
The northern Yilgarn region is poorly studied and understood hydro-
geologically and information is limited to the palaeodrainage sequences to
the southwest of our study area and some bedrock aquifers near mine water
supplies (Johnson et al., 1999). The palaeodrainage near-surface aquifer has a
low permeability with hydraulic conductivity of <2.5 m day‑1 in the dominant
alluvial clay layers. This conductivity is influenced by the presence of highly
permeable sand and gravel lenses (particularly at the base of the drainage) that
increase conductivity, as well as siliceous or ferruginous cementation reducing
permeability. Calcretes in the upper units of the palaeodrainage aquifer that
host the U mineralisation have variable permeability. Hydraulic gradients are
0.2-2 m km-1 and a preliminary estimate of groundwater residence time in
these channel systems is 100,000 years (Johnson et al., 1999). Discharge is
principally by evaporation from the playas (Commander et al., 1992), with
recharge from the palaeochannel tributaries and surface creating a continuous
groundwater flow. Residence time may be even greater in some of the
regional playas such as Lake Austin that may act as a sump with no obvious
exit palaeodrainage. The palaeodrainage system in the eastern section of the
study is linked with groundwater ultimately flowing from Lake Carey and
Lake Raeside palaeodrainage to the Eucla Basin, 350 km SE (Johnson et al.,
1999). Away from the drainage axes, the surface aquifer flow rates are varied
and not well studied, but likely to be slower as the porous channel sands
and gravels that are present in the major drainage systems (Figure 9b) are
absent (Figure 9a). The calcrete palaeochannels are major aquifers and used
as the source for watering stock, human consumption (including town water
supplies) and irrigation.
8.5 Sample results

As U mineralisation occurs as carnotite, several pathfinders were considered.
These include U, various compounds required for U to remain mobile in
groundwater or associated with mineralisation, as well as the carnotite
saturation index.
Uranium concentrations in the northern Yilgarn range from 1 to 700 µg/L
with a mean concentration of 14 µg/L. Dissolved U alone is a useful targeting
element, producing coherent anomalies near known deposits using the ~5 km
sample spacing. In particular, the greatest U concentrations are close to the
Yeelirrie deposit (6.5 and 13.7 km down drainage from Yeelirrie), identifying the
area as the strongest target, consistent with Yeelirrie being the largest known
deposit. Other known deposits also have elevated U concentrations compared
to the background.The background data was calculated on all samples greater
than 20 km from a known deposit. Results show significant differences for U
in the groundwater near the deposit compared with background.The mean U
concentration for groundwater within a 20 km radius of a deposit is 23 µg/L,
compared to 9 µg/L for background ground water concentrations. The 95th
percentile for near deposit and background groundwater U is 92 compared
to 35 µg/L, respectively. The majority of the higher U concentrations are
in the topographically lower parts of the landscape (drainage channels) and
are evident with the catchment details on the map and the Multi Resolution
Valley(MrVBF), a proxy for regolith depth and palaeodrainage (Figure 10).

A Lag
Soil
Lateritic gravel
Lateritic duricrust
Mottled zone
Clay zone
> Figure 9: A) Standard soil

profile for the study region
Saprolite
Saprock
Bedrock
B Calcrete
Quaternary / Tertiary
sands + clays
Tertiary palaeochannel
clay
Tertiary palaeochannel
sand/gravel
100 m Saprolite
Bedrock
Water table
> Figure 9: B) Soil profile

and water table level in
a paleochannel

U concentrations alone are not enough to target all areas of mineralisation: for
example, the second largest known deposit, Lake Maitland, was not identified by
U concentrations. Rather, a measurement of the carnotite saturation index (SI)
was a better indication of known mineral deposits (Figure 10). Other elements
associated with U mineralisation and transportation (e.g.V, K, P, HCO3, PO4) did
not directly indicate where known deposits were located.
Drainage divide
26°S
Meekatharra Wiluna
27°S Lake Maitland

Yeelirrie
Cue
Leinster
Sandstone
28°S
Mt Magnet
Laverton
Leonora
29°S
100 km
118°E 119°E 120°E 121°E 122°E 123°E

Carnotite SI KUO2VO4 MrVBF cover proxy index Economic uranium Water
Saturated Thick cover deposits catchments
Possibly saturated Sub-economic uranium
Close to saturated Thin cover deposits and prospect
Just undersaturated
Undersaturated
> Figure 10: Carnotite saturation index for groundwater from the northern Yilgarn.
Background is the MrVBF index shaded with the lightest areas indicative of thick cover
and wide, flat valley bottoms (palaeodrainage). Catchment boundaries, major economic U
deposits, known U deposits and U prospects are shown
8.6 Conclusion
Uranium deposits can be targeted using groundwater analysis on a regional,
multi-catchment scale. Uranium concentrations and the carnotite SI are ideal
methods for detecting secondary U deposits.

9. CASE STUDY 3: GROUNDWATER FOR NICKEL
SULFIDE EXPLORATION
Source: Gray and Noble, 2006a; Gray et al., 2009
9.1 Introduction
As target elements for nickel sulfide and volcanogenic massive sulfide (VMS)
ore deposits are readily absorbed by clays and Fe oxides, their relative
concentrations in groundwater cannot be relied on for mineral exploration.
This study examines the use of PGE and multi-element indices as pathfinders
in locating known nickel sulfide deposits.
9.2 Location
The Norseman-Wiluna greenstone belt extends through the NE Yilgarn
Craton (Figure 11) and hosts numerous major Ni deposits. The area is semi-
arid to arid and has a Mediterranean climate with hot, dry summers and
cool, wet winters. Mean annual rainfall is between 200-300 mm, similar to
the Harmony study site (Bureau of Meteorology 2010). Mulga dominates the
vegetation with minor drought resistant shrubs and grasses. The primary land
use is cattle grazing and mining.

Greenstones, including ultramafic and mafic volcanics, are enclosed within
granitoids. This greenstone belt is abundantly mineralised, hosting numerous
Ni sulfide deposits, including Cosmos, Honeymoon Well (Wedgetail, Corella,
Harrier, Hanibals), Harmony, Mt Keith, Perseverance, Prospero, Rocky’s
Reward, Sinclair, Waterloo, Weebo and Yakabindie (Six Mile Well/Goliath).
Most mineralisation is in stratiform volcanic-hosted deposits, related to
komatiite flows (Morris & Sanders 2001). The mineralisation is varied
massive, disseminated, matrix and remobilized stringer and breccia hosted
sulphide mineralisation of pentlandite and pyrrhotite. The sulfides also
contain significant concentrations of PGE. A comprehensive review of the
geology and Ni mineralisation styles and settings is given by Barnes (2006).
The topography is broadly flat with ancient alluvial transported cover of
varied thickness (a few metres to tens of metres). Soils are dominantly acidic,

sandy with red-brown hardpans and lack significant calcrete horizons except
in channels. A comprehensive review of the regolith and geomorphology of
the region is given by Anand & Paine (2002).

The watertable along the greenstone belt is 10 to 40 m below the surface.
The groundwater study included approximately 300 samples from in and
around eight deposits along 160 km of the Norseman-Wiluna greenstone
belt between Leonora and Wiluna. Gray & Noble (2006a) investigated the
evolution of groundwater and the hydrogeochemical signature related to
sulfide weathering.
9.5 Sample results

The concentration of Pt and Pd in the groundwater was determined as part
of this study using pre-concentration onto activated carbon sachets (Noble
& Gray 2010; Giblin 2001; Gray 2001). This method showed Pt and Pd (and
W) are a useful vector to Ni mineralisation. The concentrations of PGE in
the NE Yilgarn groundwater is very low (commonly <1 ng/L), making the
use of these elements as pathfinders difficult. Samples of >1 ng/L (detection)
are considered anomalous. Results show that higher concentrations of Pt, as
well as any detectable Pd, are found mostly within 2 km of mineralisation
(Figure 11). At Honeymoon Well, the four mineralised zones are all delineated
with detectable Pt (>1 ng/L, Figure 11).
The deposits all have elevated, but sporadic, Pt concentrations in the
groundwater around the deposits. The lack of a PGE groundwater signature
does not indicate an absence of Ni sulfide mineralisation (i.e. could be a false
negative), but a positive PGE result is a strong indicator of mineralisation. The
groundwater around the Jaguar VMS Zn deposit (Figure 11) is also enriched in
PGE, indicating that PGE in groundwater may be indicators of several different
types of sulfide mineralisation. The Ni sulfide mineralization in the Norseman-
Wiluna greenstone belt contains significant PGE concentrations, but the
weathering rates and mobility of PGE means concentrations are expected
to be limited. Regardless, the use of PGE is more effective than the direct
measurement of the target element (Ni for NiS deposits and Zn and Cu for

7030000 mN
Mineralization
7000000 mN 7020000 mN
Honeymoon Well
(4 deposits)
7010000 mN
Yakabindie
6950000 mN
7000000 mN
0 5 km
Harmony
# 230000 mE 240000 mE 250000 mE
Pt (ng/L)
10 - 91
6900000 mN
4-8
Waterloo
2-4
1-2
0-1
0 20 km
Geology
Ultramafic rocks
Mafic rocks
Mafic intrusive volcanics
6850000 mN Jaguar Felsic rocks
250000 mE 300000 mE
Granite rocks RNf012-11
> Figure 11 Platinum concentration in groundwater of the Norseman-Wiluna greenstone

belt in the NE Yilgarn, with a more detailed depiction of the Honeymoon Well area. Grid
coordinates are UTM Zone 51, GDA 94.

the VMS deposits) alone. Even more consistent anomalies can be observed
by combining elemental data. Thus, the NiS index (combining rescaled data of
Ni, Co, Pt and W results) very strongly delineates the Ni sulfide ore-bodies
along the belt (Figure 12).
6935000 mN
0 2 km
7000000 mN
6930000 mN
6950000 mN
6925000 mN
265000 mE 270000 mE
NiS Index
6900000 mN
> 0.85 0.40 - 0.60
0.75 - 0.85 < 0.40
0.60 - 0.75
Geology
Ultramafic rocks
0 20 km
Mafic rocks
Mafic intrusive volcanics
6850000 mN Felsic rocks
250000 mE 300000 mE Granite rocks DGf001-11
> Figure 12: NiS Index (Ni+Co+Pt+W) in groundwater of the Norseman-Wiluna

greenstone belt in the NE Yilgarn, with a more detailed depiction of the Harmony NiS
deposit and adjacent exploration to the north

Chromium in groundwater may be used to indicate underlying ultramafic
lithologies in this region (Gray & Noble 2006). Chalcophile elements (i.e. As,
Mo, Ag, Sb, W, Ti and Bi) are commonly enriched and more mobile in neutral
groundwater in direct contact with weathering sulfides, suggesting regional
groundwater sampling may be effective at locating these types of deposits.
9.6 Conclusion
PGE, in conjunction with target elements, have been shown to be useful
pathfinders in nickel sulfide and VMS deposit exploration.

10. QUICK REFERENCE GUIDES
10.1 Standard Abbreviations For Sampling
1, 2, 3, 4 - use always. 5, 6 as required
1 SB: Still Bore
SW: Still Well
FB: Flowing Bore
FW: Flowing Well
2 MP: Metal stem

PP: Poly stem
CP: Clear (assumed if not coded)
3 O: Open
C: Closed
4 V: vertical (assumed if not coded)

A: angled ... Or
deg: estimated angle
5 U: Outflow return to well from tank

(outflow under inflow)
A: Outflow return to well from tank
(outflow above inflow)
6 S: Sampled from outflow

B: Bailed from flowing windmill
(access, no wind etc)
10.2 Materials
• Bailer on retrieval cord • Eh meter and electrodes
• Bucket • Eh calibration solutions
• 25 mL HDPE bottles (3 per site) • Extra KCl electrode storage solution
• 1 L HDPE bottles (1 per site) (if used)
• Permanent marker • Carbon sachets (1 per site)
• DI water • NaCl (10 g per site)
• Thermometer • Filtration unit
• pH meter and electrodes • Spare filters
• pH calibration solutions • GPS unit
• EC meter and electrodes • Stationary for recording observations
and results
• EC calibration solutions

10.3 General sampling and testing methods flowchart
Take notes of site
Determine depth Calibrate electrodes
Discard Bail initial sample Rinse electrodes
Discard
Bail ~ 2 L of water Measure pH Eh EC
Fill 1000 mL bottle #4 Set up filter Fill alkalinity bottle #2
To laboratory –
Add C and NaCl Filter ~ 50 mL
titrate for HCO3
Shake 7 days Pour to anions bottle #1
To laboratory for IC
Remove and dry C Discard extra filtrate
anions analysis
Measure volume Filter ~150 mL
To laboratory for Use 5 mL to rinse

weighing, ashing, cations bottle
aqua regiadigestion
and analysis by
ICPMS/OES Pour to cations bottle #3
To laboratory
Acidify for ICPMS/OES
cations analysis

11. ACKNOWLEDGEMENTS
This Hydrogeochemistry Field Guide presents research conducted by CSIRO
scientists, Dr David Gray and Dr Ryan Noble, as well as many of their CSIRO
colleagues at the Australian Resources Research Centre (ARRC) in Perth,
Western Australia. The field guide is a culmination of research conducted
through CSIRO’s Minerals Down Under Flagship, CRC LEME and DET CRC.
Many thanks go to them for their support, proofing and guidance in assembling
this Guide. Special thanks to Alan Gill, a science communication student from
The University of Western Australia’s Science Communication program, for
compiling and pulling together all the vital material required to produce this
publication.

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samples? At test Covering 62 elements and four bottle types: high density
polyethene (HDPE), polypropene (PP), fluorinated ethene propene
copolymer (FEP) and perfluoroalkoxy polymer (PFA). The Science of the
Total Environment, 239, 111-130
Reiman, C., Grimstvedt, A., Frengstad, B. & Finne, E. 2007. White HDPE bottles
as source of serious contamination of water samples with Ba and Zn.
Science of the Total Environment, 374, 292-296
Robertson, I.D.M. 2001. Geochemical exploration around the Harmony
gold deposit, Peak Hill, Western Australia. Geochemistry: Exploration,
Environment, Analysis, 4, 113-127
Williams, I.R. 1975. Eastern Goldfields province. In: Geology of Western
Australia. Western Australia Geological Survey Mem 2, 33-55

13. GLOSSARY
13.1 Abbreviations
CRC LEME Cooperative Research Centre for Landscape Environments
and Mineral Exploration
DET CRC Deep Exploration Technologies Cooperative Research
Centre
DI deionised
DOC dissolved organic carbon
EC electrical conductivity
Eh oxidation/reduction potential
HDPE high density polyethylene
IC ion chromatography
ICP-MS inductively coupled plasma mass spectrometry
ICP-OES inductively coupled plasma optical emission spectrometry
MrVBF multi-resolution index of valley bottom flatness
PGE platinum group elements
RAB rotary air blast
RC reverse circulation
SI saturation index
VMS volcanogenic massive sulfide

13.2 Elements/Compounds
Ag silver HCl hydrochloric acid Pt platinum
As arsenic HCO3 bicarbonate Rb rubidium
Al aluminium Hg mercury Re rhenium
Au gold In indium Sb antimony
B boron K potassium Sc scandium
Ba barium KCl potassium chloride Se selenium
Be beryllium La lanthanum Si silicon
Bi bismuth Li lithium Sn tin
Br bromine Mg magnesium SO4 sulphate
C carbon Mn manganese Sr strontium
Ca calcium Mo molybdenum Ta tantalum
Cd cadmium Na sodium Te tellurium
Ce cerium NaCl sodium chloride Th thorium
Cl chlorine Nb niobium Ti titanium
Cs caesium Nd neodymium U uranium
Co cobalt Ni nickel V vanadium
Cr chromium NO3 nitrate W tungsten
Cu copper P phosphorous Zn zinc
F fluorine Pb lead Zr zircon
Fe iron Pd palladium
Ga gallium PO4 phosphate
13.3 Units
Distance/Size Mass Concentration
km kilometres g grams v/v volume per volume
m metres mg milligrams M molar concentration
cm centimetres µg micrograms (1M = 1 mol L-1)
mm millimetres ng nanograms mg/L milligrams per litre
µm micrometres µg/L micrograms per litre
Measurements
Volume ng/L nanograms per litre
mS milliSiemens
L litres µS microSiemens
mL millilitres mV millivolts

MINERALS DOWN UNDER (MDU) FLAGSHIP EXPLORATION
AND TECHNOLOGY GUIDES
This series is designed to help mineral explorers understand and work
more efficiently and successfully in the Australian environment where access
and consistent sample media can be difficult to obtain and regolith cover
commonly masks ore deposits.
This guide is the first in a series of MDU Exploration and Technology Guides
which complement the previously published CRC LEME Explorers’ Guide
series.
The field guide demonstrates applied hydrogeochemistry and highlights the
robust, relatively inexpensive and straight forward methods of groundwater
sampling to explore for mineral deposits across Australia.
Using the guide – The field guide has a number of sections covering:
• The purpose, background, limitations and benefits of hydrogeochemistry
(Sections 1 and 2)
• The sources of groundwater, specific materials, methods and analytical
steps (Sections 3 to 6)
• Case studies with applied examples of hydrogeochemical exploration
for Au, U and Ni deposits (Sections 7 to 9)
There are quick reference guides with a glossary at the back.
MDU Discovery Theme objective: to drive exploration success and reduce

the significant risks and costs associated with mineral exploration, the Flagship
provides an integrated research and development program that focuses on the
unique challenges of the Australian landscape and its geological endowment
and architecture.
Series Editor: Ryan Noble

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MDU Flagship Exploration and Technology Guide

FIELD GUIDE FOR MINERAL

Cooperative Research Centre for

1. Mineral exploration 2. Geochemistry 3. Groundwater

Epublish Report Number: EP113936

Editor: Alan Gill

Copy editors: David Gray, Ryan Noble and Indra Tomic

Series editor: Ryan Noble

Hydrogeochemical analysis: Field Guide i

2. Overview: Mineral exploration using hydrogeochemical analysis . . . 3

Hydrogeochemical analysis: Field Guide iii

7. Case Study 1: Harmony gold deposit . . . . . . . . . . . . . . . . 21

8. Case study 2: Groundwater Uranium from farm wells and bores . . 25

9. Case Study 3: Groundwater for nickel sulfide exploration . . . . . . 31

10. Quick reference guides . . . . . . . . . . . . . . . . . . . . . . . 37

iv Hydrogeochemical analysis: Field Guide

Hydrogeochemical analysis: Field Guide v

Hydrogeochemical analysis: Field Guide 1

1.3 Exploration targets

Ore group Associated elements

2 Hydrogeochemical analysis: Field Guide

Hydrogeochemical analysis: Field Guide 3

Groundwater Advantages Disadvantages

Hydrogeochemical analysis: Field Guide 5

3.2 Bores/drill holes

6 Hydrogeochemical analysis: Field Guide

4.1 Water collection

Collection Advantages Disadvantages

4.2 Sample storage and filtration

8 Hydrogeochemical analysis: Field Guide

> Figure 4: Filtration equipment

Hydrogeochemical analysis: Field Guide 9

4.4 Field measurement chemicals

10 Hydrogeochemical analysis: Field Guide

> Figure 5: Carbon sachet

Hydrogeochemical analysis: Field Guide 11

5.2 Site investigation

5.3 Prepare equipment and filtration unit

Hydrogeochemical analysis: Field Guide 13

5.4 Prepare and label bottles

5.5 Sample groundwater

5.6 Chemical analysis in the field

14 Hydrogeochemical analysis: Field Guide

5.7 Filtered sample collection

5.8 Unfiltered sample collection

Hydrogeochemical analysis: Field Guide 15

Element/ Method Detection limit Units

> Table 4: Typical detection limits for anions

6.2 Alkalinity analysis

Hydrogeochemical analysis: Field Guide 17

Element/ Method Detection limit Units

18 Hydrogeochemical analysis: Field Guide

6.4 Gold/Platinum group elements analysis

Element/ Method Detection Units

6.5 Mapping and interpreting results

Hydrogeochemical analysis: Field Guide 19

118°E 119°E 120°E 121°E 122°E

20 Hydrogeochemical analysis: Field Guide

7.3 Regolith characteristics

Hydrogeochemical analysis: Field Guide 21

Palaeochannel Groundwater flow direction

> Figure 7: Dissolved Au and Mo concentrations in groundwater superimposed over

7.4 Groundwater depth and chemistry