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Chapter 11
Sampling, Analysis
and Quality Control
11.1. ERRORS IN SAMPLE important topic of sampling covered elsewhere in
PREPARATION AND ANALYSIS
Geologists should be aware of the many factors
that can adversely affect the quality of analytical
results reported by laboratories and should
strive to minimise, if not eliminate, these by
implementation of rigorous quality control
programs and consultation with laboratory
personnel. When implemented, a traceable quality
assurance/quality control (QA/QC) program
provides accountability, reduces uncertainty
in ore reserve calculations and adds value to
projects.
There are errors inherent in all three stages
of the data acquisition process, from the initial
in situ field sampling through to laboratory
sample preparation and analysis. Gy’s formula
has led to a greater understanding of the various
sources and magnitude of these errors and has
been discussed in detail by Gy (1992) and Pitard
(1993).
Sampling errors
Sampling errors occur during the in situ (field)
sampling of media (soil, sediment, outcrop, drill
core, reverse circulation cuttings or vegetation).
The intention of sampling is to obtain a sample
compositionally representative of a finite volume
of the surrounding sample medium. The errors
associated with sampling will vary depending on
the distribution of the metal of interest and are
generally higher in precious metal ores (nuggety
high-grade ores in particular) compared with
base metal ores. The reader is referred to the
Chapter11.indd 311
this monograph and should be mindful of the fact
that, of the numerous sources of error associated
with the analysis of geological materials, the
initial field sampling is widely accepted as being
the greatest source of error (James and Radford,
1980).
Sample preparation errors
The intent of sample preparation is the reduction
in particle size, through crushing and pulverising,
and in sample size, through splitting, while
retaining representivity. Samples as large as 10 -
30 kg are frequently presented to the laboratory
for preparation and the final analysis is of a
portion as little as 0.2 g. The expectation is that
the result obtained on this 0.2 g aliquot is, within
acceptable limits, representative of the original
field sample.
Drying
All samples are dried as the first stage in sample
preparation at temperatures of 105 or 110°C
(note: quarantine regulations stipulate that
some samples originating from overseas be dried
at 160°C for the purpose of sterilisation; these
regulations can vary from one jurisdiction to
another). Drying is generally for a minimum of
six hours or until constant mass is achieved. For
sulfide-rich samples, drying temperature may be
reduced to 65 - 75°C to minimise oxidation. This
precaution is critical for mineralised samples
where pyrrhotite is the major sulfide as this
mineral is susceptible to auto-combustion when
heated in a drying oven or even during grinding.
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 CHAPTER 11 – SAMPLING, analysis and quality control
Where hygroscopic moisture is not completely
removed assay results will bias low by an amount
equivalent to the weight per cent residual
moisture.
In the case of heat sensitive materials, such as
coal and sulfides of mercury, arsenic, antimony
and bismuth, care should be exercised to avoid
overheating during drying as this may lead
to volatile losses and changes in chemical
composition and speciation. Gypsum can also
lose crystalline moisture at temperatures as low
as 90°C.
Crushing
It is important that crushing and splitting
equipment is cleaned properly between each
sample to minimise cross contamination. Losses
of fines should be kept to a minimum as these
may be compositionally distinct from the coarse
fraction and bias the sample. Samples and rejects
can be weighed at each stage of the size reduction
process to monitor these losses. Crushing to at
least 80 per cent (preferably 90 per cent) minus
2 mm is desirable to minimise sampling error
during splitting.
Splitting
The particle size of the crushed sample should be
fine enough to permit splitting of a representative
sample for pulverising. Splitting is generally by
riffle, cone or rotary divider. Where sample size is
less than 3 kg a ‘total sample prep’ is sometimes
employed. This involves bypassing the splitting
stage and pulverisation of the entire sample in a
larger capacity bowl. Smee and Stanley (2005)
consider this inferior to splitting off a 1 kg or
smaller portion for grinding as the particle size
reduction (comminution) of a 3 kg pulverised
sample can be substandard.
TABLE 11.1.1
Bowl type Sample capacity
Standard mild steel bowl to 3.5 kg
Cr-free steel 500 g to 3 kg
Zirconia 100 g
Tungsten carbide 150 g
Agate 100 g
Source: SGS, 2011.
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Chapter11.indd 312
Pulverising
The grind should be at least 85 per cent passing
75 microns to maximise recovery by the chosen
method and to achieve a homogeneous pulp
for subsampling. Appropriate grind size will
depend on the characteristics of the material
being ground, but is particularly important
where the metal(s) of interest are present in low
concentration and comprise a major component
of a trace mineral, eg zircon in a basalt. Sample
size will dictate bowl size and where various sized
samples are submitted they may be pulverised
in different bowls. This has implications for the
monitoring of contamination with coarse blanks.
Cross contamination from material adhering to
the grinding bowl can be minimised by inclusion
of a quartz (or other barren material) wash or
alcohol wipe between samples if air blowing is
insufficient. For iron ore samples a quartz wash
is not recommended as this will contaminate the
sample more than an iron ore sample due to the
chemical contrast. For gold analysis the sampling
error depends on the number and size of gold
particles in the aliquot for analysis. Gold, being
malleable, may not undergo much comminution
so fine grinding may not improve the sampling
error.
Crusher and mill contamination
Wear in the crushing and grinding media
(bowl, puck and rings) is another source of
contamination. Mill contamination depends on
the type of mill being used. See Table 11.1.1.
Subsampling for analysis
A portion (generally 100 - 200 g) of the bulk
pulp is transferred to a pulp packet from which
the assay portion is taken for analysis. The
amount analysed may be 25 - 50 g for fire assay
of precious metal ores to as little as 0.2 - 1 g for
an acid digestion of base metal ores. Steps should
Main contaminant Minor contaminant
Fe, Cr Mo
Fe Mn
Zr, Hf Al
W, Co (Ta)
Si
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 CHAPTER 11 – SAMPLING, analysis and quality control
be taken to ensure that the pulp is homogeneous
before taking an aliquot for analysis to keep the
subsampling error within acceptable limits. If
a subset of pulp samples are submitted to an
external check laboratory for analysis the check
laboratory should be instructed to re-homogenise
the pulps prior to subsampling for analysis. This
step overcomes possible segregation that can
occur during transport and can be achieved by
mat rolling or re-pulverising.
Mislabelling
Many laboratories use bar coding to eliminate
transcription errors in sample identification.
Labelling errors generally occur at the point
of sample collection and tagging or at the
laboratory, when the initial batch/job set up is
done. The submission of sample lists in electronic
format can help reduce labelling errors in cases
where samples are not submitted with bar codes
already in place. Related sample preparation
errors include unintentional mixing of fractions
of different samples. The more complex the
analytical scheme (eg fire assay compared with
acid digest) the greater the chance of mislabelling
in the laboratory.
Analytical errors
Analytical errors, also referred to as measurement
errors, are sources of error originating from the
point of weighing of the analytical subsample,
through the digestion process and instrumental
reading, to the final reporting of results.
Drying and weighing
For highly hygroscopic materials, such as some
nickel laterite ores and iron ores, a further drying
stage is required immediately prior to weighing
the portion to be analysed. The sample should be
dried at 105°C until constant weight is achieved
then transferred to a desiccator, containing fresh
desiccant, to allow to cool to ambient temperature
prior to weighing. Alternatively, the sample can
be left to obtain hygroscopic equilibrium in the
laboratory atmosphere and a separate sample
taken for moisture determination. The results
are then corrected to a dry basis based on the
moisture content. It should be stressed that
incomplete drying or inadequate correction for
moisture can be a major source of error in the
analysis of hygroscopic materials such as goethite
iron ores and laterites.
Chapter11.indd 313
Inappropriate method selection
The choice of analytical method should be made
in close consultation with laboratory personnel.
For many sulfide-hosted base metal ores an aqua
regia digest may give total recoveries, but silicate-
hosted nickel, for example, will require four acid
(where hydrofluoric acid is added to dissolve
silicates) or fusion treatment to report the total
nickel. Fusion methods are required for metals
(such as Sn, W, rare earth elements (REE), Ti,
V) that may be hosted in refractory minerals
and for whole-rock major element oxides. As a
general rule, the more aggressive the digestion
(aqua regia four acid lithium borate/
sodium peroxide) the higher the lower limit of
detection (LLD) and the lower the sensitivity.
Ideally the LLD should be at least 20 times below
the expected concentration level. Where this is
unknown a good rule of thumb for geochemical
prospecting is to have the detection limit ten per
cent of crustal abundance (Clark value). For gold,
lead collection fire assay and neutron activation
analysis will give total concentrations, whereas
recoveries by aqua regia and cyanide leach may
be compromised by the presence of fine-grained
gold included in silicates and sulfides (cyanide
leach).
Geochemical versus ore grade methods
For soil and stream sediment surveys and
exploration drilling, geochemical or low level
methods are generally suitable. Lower limits of
detection are well below the lower concentration
range of most geological materials and upper
limits for base metals are around one per cent.
An accuracy of ±10 per cent for geochemical
methods is usually quoted by laboratories and is
considered ‘fit for purpose’ in these applications.
For resource work accuracy is critical and ore
grade methods are employed. These methods use
volumetric glassware and superior QC and an
accuracy of ±5 per cent is generally quoted. Many
laboratories offer the convenience of analysing
variably mineralised samples by geochemical
methods and automatically reanalysing samples
above the upper limit of detection by an ore
grade method. This protocol can be set up in
consultation with the laboratory manager. For
commodities such as copper, where cut off grades
are less than one per cent, the laboratory can be
instructed to reduce the changeover to 0.5 per
cent or less to ensure the quality of results.
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 CHAPTER 11 – SAMPLING, analysis and quality control
Precision errors are dependent on analytical
method and concentration and increase
dramatically as the lower limit of detection is
approached. For example, precision of 100 per
cent is acceptable at the detection limit for ore
grade digests.
Voluming
Following acid digestion or fusion the sample is
dissolved by leaching with HCl and then made
up to constant volume (eg 100 ml) by dilution
with distilled water. Additional dilutions may
be required before the solution is then drawn
into the reading instrument for analysis. If the
glassware and pipettes are poorly calibrated,
non-volumetric or the operator careless, then
dilution errors will result. For example, voluming
to 101 ml instead of 100 ml can produce a one per
cent negative bias in the result.
Instrument calibration
Poor instrument calibration will generate bias in
every sample of an analytical batch. This run bias
is a large source of systematic error in analytical
chemistry. Ensuring that the uncertainty on the
calibration is small will minimise this source of
error. Instruments are calibrated using standard
solutions prepared from spectrographically pure
chemicals. The levels of analytes in the calibration
solutions should be in the appropriate range
and similar to the samples to be measured. The
solutions are made up at regular intervals and
at different grades appropriate to a particular
method. Once depleted, new solutions are
prepared. Provided these are made up with the
proper pipettes and using excellent standard
solutions the uncertainty on the final solution
concentrations should be small in comparison
with the calibration uncertainty.
All laboratories exhibit a degree of run-to-run
bias. It is the responsibility of the laboratory
operator to ensure, through internal QC
protocols, that this bias is within acceptable
limits. The geologist should also monitor this by
insertion of appropriate reference materials.
Instrument stability
Can be adversely affected by drift or noise. Drift
occurs when the instrumental response to a
given concentration of analyte or to background
conditions varies with time (Bloom, 2002).
The drift may not be linear or progressive
and is frequently the result of a change in
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ambient temperature or warming up of the
electronic components of the instrument during
operation. Progressive blocking of nebulisers
or atomisation sources are a physical cause of
drift. If unrecognised, the results will be biased.
Internal standards and normalisation standards
can be used to minimise the effects of drift
(Bloom, 2002).
Noise is short-term instability of the
instrument and hence signal. It can be the result
of variation in atomisation and nebulisation
conditions or due to the electronic components.
The noise of the instrument is a major factor
in governing detection limits, as the noisier the
instrument, the higher the detection limit. This
parameter can be used to monitor degradation of
instruments or components.
Memory effect
If analyte concentrations in successive samples
fluctuate widely (over several orders of
magnitude) the lines (tubing) of the reading
instrument can become contaminated. The
sample, or samples, immediately following the
sample with elevated concentration will be
biased high due to this carry over effect unless
the lines are thoroughly flushed by the operator.
Pulp blanks can be used to monitor this potential
problem. Gold is ‘sticky’ in peristaltic tubing
and thus prone to carryover. This is a very good
reason not to submit ore grade gold CRMs in
trace gold jobs.
Inter-element interferences
Due to the presence of constituents in the
sample at concentrations sufficiently elevated to
interfere with the measurement of an analyte of
interest. The effect of the interference may lead
to either positive or negative bias in the analyte
and may be chemical or instrumental in nature.
Crucible contamination
There is an increasing tendency for commercial
laboratories to offer analysis of base metal sulfide
ores by lithium borate fusion X-ray fluorescence
(XRF). The platinum crucibles used in the fusion
can become contaminated by alloying of metals
over time and this degradation can be a source of
cross contamination.
Nickel, zirconium and ceramic crucibles are
used for sodium peroxide fusions. These fusions
cannot be used for the determination of:
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 CHAPTER 11 – SAMPLING, analysis and quality control
•• sodium;
•• the metal from which the crucible is
manufactured and other metals, which may
be present in the crucible in significant
amounts; or
•• elements subject to spectral interference by
these elements.
For example for zirconium crucibles zirconium,
hafnium and phosphorus cannot be determined,
(and rare earth elements are not advisable)
whereas for nickel crucibles nickel, cobalt and
molybdenum cannot be determined and the
analysis of chromium, copper, manganese and
zinc is not recommended (Genalysis, 2011).
Dilution errors
When analyte concentrations exceed the upper
limits for particular methods they can be brought
into range by dilution of the digestion liquor.
The degree of dilution needs to be performed
accurately and the appropriate dilution correction
calculations made. A preferred strategy is to
re-assay with a technique appropriate for the
concentration range.
Terminology
Accuracy – the closeness of agreement between
a test result and the ‘true’ value or accepted
reference value. The term accuracy, when applied
to a set of test results, involves a combination of
random components and a common systematic
error or bias component. Accuracy is related to
both trueness and precision (ISO 1993 and 1994).
Precision – the closeness of agreement
between independent test results obtained under
stipulated conditions. Precision depends only on
the distribution of random errors and does not
relate to the true value or the specified value.
The measure of precision is usually expressed in
terms of imprecision and computed as a standard
deviation of the test results (ISO 1993, 1994 and
2004).
Trueness – the closeness of agreement between
the average value obtained from a large series
of test results and an accepted reference value.
The measure of trueness is usually expressed in
terms of bias (ISO 1993, 1994 and 2004). Note:
previously this definition applied to ‘Accuracy’
and this meaning is still in widespread use in
current literature.
In summary in ISO usage, trueness refers to
being centred properly (but without regard to
Chapter11.indd 315
dispersion), precision refers to tightness of results
(without regard to centring), and accuracy covers
both (on centre and tightly together) (Hauck et
al, 2008). Figure 11.1.1 illustrates the meaning of
these terms.
Figure 11.1.1
Schematic diagram illustrating the relationship
between trueness, precision and accuracy (from
Flynn and Holdsworth, 2009).
Bias – the difference between a test result or the
mean of a series of test results and the accepted
reference value. It is the inverse of trueness
and is either expressed in absolute terms in the
reporting unit of measure or as relative per cent
(positive or negative).
Geological blank – a field sample or
prepared pulp sample that contains very low
or undetectable concentration of the element
being sought. The field or coarse blank measures
contamination in both the sample preparation and
analytical stages, while the pulp blank measures
contamination in the analytical stage only. Care
should be taken when inserting coarse blanks to
monitor possible carry over contamination from
specific high grade samples, as the crushing and
pulverising sequence varies between laboratories
and even within laboratories, depending on
the mills and preparation schemes (robotic or
manual) used.
Reagent blank – the concentration of the
element of interest in the digest solution or
fusion bead without the addition of the sample.
It is a measure of the contamination contributed
by reagents.
Analytical blank – a combination of the reagent
blank and the signal component attributable to
instrument noise.
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Certified reference material (CRM) – a
reference material for which one or more
parameters have been certified by a technically
valid and recognised procedure and for which a
certificate or other valid documentation has been
issued by a certifying body (ISO 2006).
Matrix-matched certified reference material
(MMCRM) – a CRM prepared from geological
material of identical source to the samples being
monitored. It has the advantage of having the
same mineralogy and chemistry and hence
similar digestion and analytical characteristics.
Reference material (RM) – material for
which one or more parameters are sufficiently
well characterised to be used for the calibration
of instruments, the assessment of analytical
methods, or for assigning values to unknown
materials.
Standard reference material (SRM) –
synonymous with reference material (note: in
the past this acronym has also been used for
‘secondary reference material’ – a material
characterised to a lower level than and generally
not conforming to all ISO criteria for a CRM).
Standard – literally this refers to a recognised
and approved method or procedure (such as the
standards published by ISO) but its use to describe
reference materials is also well entrenched in the
mineral and chemical industries.
Pigeon pair, paired offsets, bracketed
standards, variance standards – terms used
to describe a pair of CRMs of almost identical
matrix that differ in concentration of one or more
certified elements by an amount approximating
the typical measurement error of methods
in common use at commercial analytical
laboratories.
Certified value – a statistically robust
estimate of the true value of a reference material
parameter (equivalent to the recommended
value for a CRM).
Recommended value – a statistically robust
estimate of the true value of a reference material
parameter (equivalent to the certified value for
a CRM).
Inferred or informational value – an
uncertified approximation of a reference material
parameter, generally derived from results of
fewer than six laboratories.
Ninety-five per cent confidence interval –
an interval for which we can assign a 95 per
cent probability that the recommended or
certified value lies within; alternatively, we can
316 Field Geologists’ Manual
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say that 95 per cent of all confidence intervals
determined in a like manner (from different
samples of the population) will include the
recommended or certified value. It is important
to note that the 95 per cent confidence interval is
unrelated to control limits (ie it is not equivalent
to two standard deviations of the recommended
value). It is a measure of the reliability of the
recommended value; generally the narrower the
confidence interval the greater the certainty in
the recommended value.
Control limits – a window of acceptability for
results obtained by a laboratory for a reference
material and generally calculated from multiples
of the standard deviation of the certification
data. There are a number of methods in
use for the determination of the standard
deviation as applied to control limits. Ideally
standard deviations should include within-run
(repeatability) errors and between-run errors.
Determination of between-run errors require
a temporal aspect to the certification program
(ie submission of two or more batches to the
participating laboratories at timed intervals).
Where between-lab (bias) errors are included
the calculated standard deviations will be larger
than those calculated solely from within- and
between-run errors.
Repeatability – the closeness of agreement
between results for the same parameter carried
out by the same method, by the same operator,
with the same instrument, in the same laboratory,
over a short interval of time.
Reproducibility – the closeness of agreement
between results for the same parameter carried
out by a different method, or different operator,
or different instrument, or in a different
laboratory, or over an interval of time quite
long in comparison to the duration of a single
measurement.
Field duplicate – a second split of drill core,
reverse circulation cuttings, outcrop, soil or
stream sediment from the same sampling interval
or area and collected using the same procedure.
They are bagged and numbered separately to the
primary sample so as to be blind to the sample
preparation laboratory. Field duplicates contain
all sources of error: the original in situ sampling
error, sample size reduction error, subsampling
error at the pulp level and analytical error. They
can be used to determine the combined field,
preparation and analytical precision.
Preparation duplicate – a second split taken
after crushing but before pulverising. If the
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 CHAPTER 11 – SAMPLING, analysis and quality control
crushing procedure is two-stage, preparation
duplicates should be taken at each stage. These
are normally taken routinely by the lab at a
frequency of one in 40 samples. They contain the
error of sample size reduction and analysis.
Pulp duplicate – a second weighing and
analysis from the same pulp and usually done
routinely by labs at a frequency of one in five to
one in 20 samples. The pulp duplicate has the
errors of analysis (including subsampling and
weighing errors).
Re-reads – subsequent instrument readings
from the same digestion solution as analysed
initially. These measurements have instrument
(and possibly final dilution) errors only. Re-
reads are generally performed by the laboratory
to check specific problems and the results are not
generally reported to the client.
Lower level of detection (LLD) or detection
limit (DL) – the lowest concentration of an
element that can be detected with a 95 per cent
probability. It is calculated by taking a large
number of instrumental readings at or near the
blank level, calculating the standard deviation
and determining the value corresponding to
two or three standard deviations plus the blank
value (Bloom, 2002; H Waldron, 2011, personal
communication).
Upper limit (UL) – the highest concentration
of an element that can be quantified by a
particular analytical method. It coincides with
the high end of the calibration range of the
reading instrument and may also be governed by
digestion and recovery limitations.
Sensitivity – refers to instrumental reading
resolution and is closely related to, but distinct
from, the detection limit. Generally, the higher
the sensitivity the lower the detection limit and
vice versa. The sensitivity of a technique relates
to the slope of the calibration graph, it is the
slope of the relationship between instrument
signal and analytical concentration. For example,
an ore grade method may report to the nearest
0.01 per cent (100 ppm), compared with a low
level method reporting to the nearest 0.0001
per cent (1 ppm). It is customary to report base
metals in weight per cent when determined by
ore grade methods and in ppm (or ppb) when
analysed by low level (geochemical) methods.
Quality assurance (QA) – refers to all planned
or systematic actions necessary to provide
adequate confidence that a product or service will
satisfy given needs (Kirschling, 1991). Assurance
Chapter11.indd 317
in the quality context is the relief of concern
about the quality of a product (Vaughn, 1990).
Quality control (QC) – is one component of
quality assurance. It is a system of measures
intended to ensure that a product or service
adheres to a defined set of quality criteria, or
meets the requirements of the customer or client.
Random errors – errors inherent in all
methods of analysis due to fluctuations in
measurement resulting from unstable power
supplies, instrument noise, non-reproducible
atomisation, plasma fluctuations, X-ray intensity
variation and voluming solutions (human error
component). Random errors impose a limit on
analytical precision and while they can never be
eliminated, they can be minimised and quantified
by replicate measurement of the same sample.
Systematic errors – errors arising from
matrix effects peculiar to a specific technique or
lithology, pronounced compositional differences
between sample and CRM, incorrect instrument
calibration, human bias due to preconceived
notion of expected grades of CRMs run with
sample batches. CRMs unfamiliar to the analyst
are the best way to monitor bias introduced
through systematic errors.
Gross errors – errors of substantial magnitude
mostly originating from human error. They
are random in nature and include incorrect
numbering of samples in the field, inadvertently
interchanging samples during analysis (eg
sample swaps in fire assay), miscalculation of
the final result and other randomly introduced
human errors. They can be detected and rectified
with appropriate quality control procedures such
as submission of blanks, duplicates and CRMs
with each batch of samples.
Quality control
A sound QA/QC program is the cornerstone of all
well-managed exploration projects and mining
operations. It involves the monitoring of sample
quality and measurement of analytical bias and
precision. Analytical bias is primarily quantified
by the use of certified reference materials and
secondarily by the check assaying of a subset
of samples at a second external laboratory.
Precision is quantified by the use of field,
preparation and pulp duplicates. Quality control
entails monitoring laboratory performance by
acquisition of appropriate QC data followed by
critical evaluation.
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Data acquisition
The following procedures should be implemented
prior to submission of sample batches for analysis.
Blanks should be inserted at regular intervals
in the sample stream to monitor contamination.
Coarse blanks consisting of crushed barren
material are subjected to the entire sample prep-
aration process and therefore able to monitor
cross contamination in crushing, splitting and
grinding apparatus. Pulp blanks can be used to
monitor contamination during sample digestion
and measurement. As blanks are geological
materials they contain trace amounts of most
elements, hence it is important that the material
selected is appropriate and that control limits are
set at sensible levels.
Coarse blanks are often inserted after
mineralised samples where the risk of
contamination is greatest. Waldron (2011,
personal communication) recommends that
geologists be familiar with the preparation
routine of their laboratory if specific positioning
of coarse blanks is critical. For example, manual
preparation staff frequently work with two
pulverisers simultaneously, so each alternate
sample will be prepared in a separate mill. A blank
inserted to immediately follow a high sample
would therefore be milled in the other mill.
Robotic preparation uses up to six mills with the
first available one being used. In addition, mill
selection is based on capacity and sample size.
Blanks are often submitted in smaller amounts
and consequently may not be pulverised in the
same larger mills as the samples, thus rendering
the monitoring process ineffective.
Field, preparation and pulp duplicates should
be regularly taken and analysed to confirm the
veracity of field sampling and sample preparation
and subsampling protocols.
Routine lab versus check lab – five to ten
per cent of samples should be re-assayed by a
second unrelated laboratory for comparison
with the routine laboratory’s results. If there
are discrepancies, analyses at a third or umpire
laboratory may be required. External check
analyses can be done using the same pulp
packet as was originally analysed, or on a second
pulp split. It is often wise to prepare for inter-
laboratory checks by requesting a second pulp
split be taken, at a set frequency, during initial
sample preparation. This split can be set aside
until required for external check analyses.
Recovering excess pulps from storage and
splitting off a second portion at a later date
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can be time consuming and therefore costly.
Misidentification of samples can also add to
sources of error.
Insertion of certified reference materials
(CRMs) or matrix-matched certified reference
materials (MMCRMs) into the sample stream
at a frequency of one in 20 or 30. CRMs are
available commercially from recognised
producers. Where possible, CRMs should match
the lithology and mineralisation style of the
deposit being evaluated, as well as cover the
expected concentration range of target metals.
MMCRMs are prepared by CRM producers
from ore samples taken from the same or
similar deposit being evaluated or mined. They
are an ideal compositional and mineralogical
match and therefore better suited to resource
definition and grade control QA/QC. Key grades
are cut-off, run-of-mine (ROM) and the 90th
percentile. Low-level to lightly mineralised
CRMs are available for greenfields exploration,
soil and stream sediment geochemistry and
lithogeochemical applications. They are prepared
from oxidised or primary materials and generally
certified for a range of major, minor and trace
elements including precious and base metals,
REE and pathfinder elements.
Laboratory audits to confirm adherence to
contractual obligations and standard operating
protocols.
The flow sheet depicted in Figure 11.1.2
illustrates a typical quality control protocol for
drill core sampling, preparation and analysis.
A QA/QC program should incorporate some or
all of the following elements (Bloom, 2002):
•• submission of five to ten per cent field
duplicates,
•• submission of three to five per cent sample
preparation duplicates (approximately 90 per
cent passing 2 mm),
•• submission of three to five per cent pulp
duplicates,
•• insertion of three to five per cent of certified
reference materials (CRMs) or matrix-
matched certified reference materials
(MMCRMs),
•• randomisation of sample numbers before
submission to a laboratory,
•• comparison of multi-element trends for
elements determined by different laboratory
procedures,
•• comparison of results for the same element
determined by different methods,
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 CHAPTER 11 – SAMPLING, analysis and quality control

•• routine insertion of an unprepared barren •• analysis of five to ten per cent of sample pulps
sample (blank), at an independent check laboratory, and
•• routine insertion of a pulverised barren •• analysis of five to ten per cent of sample
sample (blank), rejects at an independent check laboratory.

Drill core sampling, sample preparation and analysis

Figure 11.1.2
Flow sheet for drill core sampling, sample preparation and analysis (modified from Bloom, 2002).

Field Geologists’ Manual 319

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 CHAPTER 11 – SAMPLING, analysis and quality control

Evaluation techniques – precision assumption of a normally distributed error, and

Scatter plots of field, preparation and pulp
duplicates offer a simple form of graphical
representation and can be used to provide a
visual comparison of precision at the various
stages of sample size reduction.
Thompson-Howarth estimate of precision
utilises the results of field, preparation and pulp
duplicates to quantify repeatability precision
(Thompson and Howarth, 1973, 1978; Stanley,
2003). Field duplicates contain all sources of
error: the original in situ sampling error, sample
size reduction error and analytical error (note:
analytical error includes subsampling and
weighing errors at the pulp level). Preparation
duplicates contain the error of sample size
reduction and analysis, while pulp duplicates
contain error of analysis only. By assembling and
evaluating the field sampling, preparation, and
pulp duplicate results, the errors associated with
each step of sample treatment can be estimated
by subtracting ‘downstream error’ from each
composite error estimate (Figure 11.1.3). The
source of the greatest uncertainty in the sampling
and analytical program can thus be quantified
and targeted for reduction through procedural
modifications, if necessary (Smee and Stanley,
2005).
According to Abzalov (2008) the Thompson-
Howarth method produces consistently lower
results than other methods as it relies on the
thus produces biased results when errors have
a skewed distribution. Abzalov instead concurs
with the proposal of Stanley and Lawie (2007)
to use the average coefficient of variation as the
universal measure of relative precision error in
mine geology applications.
Related precision estimates in common use
include plots of absolute relative difference
(ARD, AMPD) or half absolute relative difference
(HARD) versus percentile (rank) or duplicate
pair mean. A target of 90 per cent of samples
having an ARD (per cent) precision better than
20 per cent for preparation duplicates, ten per
cent for pulp duplicates and 30 per cent for field
duplicates is desirable but not always achievable,
especially with core samples. Actual values
for these parameters are grade and orebody
dependent and should be established on a case
by case basis.
Scatter plots of field, preparation and pulp
duplicates can be used to provide a visual
comparison of precision at the various stages of
sample size reduction.
Evaluation techniques – bias
The Shewart Control Chart or Statistical Process
Control (SPC) Chart is perhaps the most widely
used tool to monitor laboratory performance
(Figure 11.1.4). Reference materials are inserted
at a frequency of one in 20 to one in 30 into the

Figure 11.1.3
Modified Thompson-Howarth-type plot illustrating the magnitude of total, sampling (8 kg), preparation (1 kg)
and pulp (50 g) error, as determined by duplicate quality control monitoring from an intrusion related gold
deposit (from Smee and Stanley, 2005).

320 Field Geologists’ Manual

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 CHAPTER 11 – SAMPLING, analysis and quality control
Figure 11.1.4
Shewart control chart showing laboratory results for a gold CRM with Certified value of 2.55 g/t (green line),
two standard deviations lower and upper warning lines (orange) and three standard deviations lower and
upper control lines (red).
Results for Au in CRM (2.55g/t)
2.9
2.8
2.7
2.6
Au (g/t)
2.5
2.4
2.3
2.2
0 10
sample stream to monitor laboratory bias. The
results obtained over time for each reference
material are plotted on a time chart together
with lines corresponding to the expected value,
warning and control limits. The expected value
plus two standard deviations and expected value
minus two standard deviations are generally
referred to as the upper warning limit (UWL)
and lower warning limit (LWL), respectively. The
expected value plus three standard deviations and
expected value minus three standard deviations
are the upper control limit (UCL) and lower
control limit (LCL), respectively. These limits
are based on how much variation is expected
in the results and are multiples of the standard
deviation value provided by the producer of the
CRM. The probability of a ±3 standard deviations
failure is only 0.3 per cent and should be a rare
event and as such, considered indicative of an
anomalous occurrence worthy of investigation.
For normally distributed data ~5 per cent of
results are expected to breach the ±2 standard
deviations warning limits.
In the application of control limits it is
important that the method being monitored is
the same as that used in the original certification
of the reference material. For example, nickel
laterite CRMs characterised by lithium borate
fusion XRF will produce standard deviations
substantially smaller than those derived from
fusion inductively coupled plasma optical
emission spectrometry (ICP-OES) methods,
owing to the superior precision of the former.
Chapter11.indd 321
failure
failure
20 30 40 50
Sample Sequence
Incorrect use of standard deviations in this way
will lead to erroneous failures and unnecessary
conflict with the laboratory.
All results plotted on the chart should be
random with no patterns or trends. They should
be distributed ‘Normally’, and fit a Gaussian
‘bell’ curve. This means that around 68 per cent
of the points lie within one standard deviation
of the mean, 95 per cent of the points should
lie within two standard deviations of the mean,
and 99.7 per cent of the points should lie within
three standard deviations of the mean. It should
be noted that some elemental abundances in
geological materials have an asymmetric rather
than normal distribution. Such distributions
usually have a preponderance of low values with
a long tail of high values, imparting a positive
skewness to the frequency distribution curve.
Data for nuggety gold ores generally typify this
kind of distribution. These limitations, however,
should not apply to good quality CRMs where
results for the certified elements are expected to
be normally distributed.
If certain rules applying to randomly distributed
data when plotted on a control chart are not met
then an investigation into the causes should be
initiated. These rules are somewhat arbitrary and
are applied at the discretion of the QA/QC analyst:
•• A point lying outside the three standard
deviations limits – there is only a 0.3 per cent
chance that this is a result of a process under
control.
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 CHAPTER 11 – SAMPLING, analysis and quality control
•• Two consecutive points lying outside two
standard deviations – the probability that
any point will fall outside the two standard
deviations warning limit is only five per cent.
The chances of two consecutive points falling
outside the two standard deviations warning
limit is only about 0.2 per cent for a process
under control.
•• Five, six, seven or eight consecutive points on
the same side of the expected value – there
is an equal chance that any given point will
fall above or below the expected value. The
chances that a point falls on the same side
of the mean as the one before it is one in
two. The odds that the next point will also
fall on the same side of the mean is one in
four. The probability of getting eight points
on the same side of the mean is only around
one per cent. However, beware of hunting
for this trend in a control chart. If you have
200 points then you have 192 sequences of
eight points. The binomial probability of one
of these sequences all lying above or below
becomes very probable rather than remotely
possible (R Holdsworth, 2011, personal
communication).
•• Five, six, seven or eight consecutive points
trending up or down – the same logic is used
here as above and the above caveat applies.
•• Four of five points falling outside one
standard deviation – in normal processing
68 per cent of points fall within one sigma
of the expected value and 32 per cent fall
outside it. The probability that four out of five
points fall outside of one standard deviation
is only about three per cent. The above caveat
applies.
•• Fourteen points alternating direction – this
rule treats each pair of adjacent points as
one unit. The chances that the second point
is always higher than (or always lower than)
the preceding point, for all seven pairs is only
about one per cent. The above caveat applies.
•• Fifteen points in a row within one standard
deviation – in normal operation 68 per cent of
points will fall within one standard deviation
of the expected value. The probability that
15 points in a row will do so is less than one
per cent. The above caveat applies.
•• Eight points in a row outside one standard
deviation – since 68 per cent of points lie
within one standard deviation of the expected
322 Field Geologists’ Manual
Chapter11.indd 322
value, the probability that eight points in a
row fall outside of the one sigma line is less
than one per cent. The above caveat applies.
These rules exist to highlight when something
improbable happens in a laboratory. The
rationale is that if something happens that
is improbable due to normal causes, it has
happened due to abnormal causes. The abnormal
cause is usually a change and since change to the
product is undesirable action needs to be taken.
The standard Shewart Chart requires each
CRM to be plotted separately with concentration
on the y axis and sample sequence on the x axis.
It is often instructive to plot all CRMs on the
same chart. This is achieved by converting the
assay values to ‘z-scores’. Z-scores are calculated
by subtracting the expected value from the
analytical value and dividing it by the standard
deviation. This converts the analytical value to
standard deviation units above and below the
mean, so all standards can be compared on the
same plot.
Box and whisker plots provide a means
of graphically comparing the distribution
characteristics of results from the primary and
external check laboratories. The five parameters
displayed on these plots are the 25th and
75th percentiles forming the bottom and top
of the box, respectively, the 50th percentile
forming a band near the middle of the box,
and the minimum and maximum of the range
of values forming the ends of the lower and
upper whiskers, respectively (Figure 11.1.5).
To eliminate the influence of outliers the 2nd
and 98th percentiles can be substituted for the
minimum and maximum values.
Scatter and relative difference plots
compare the original assays with those of the
check laboratory. In scatter plots the element
concentration of the primary laboratory (x axis)
is plotted against that of the check laboratory
(y axis). The paired results should lie along a
45° line corresponding to a 1:1 relationship,
with departures indicating bias at one or both
laboratories. Linear-scaled plots highlight the
higher values and log-scaled plots provide detail
at lower concentrations. In relative difference
plots the per cent relative difference between the
primary and check laboratory assays (y axis) are
plotted against the mean concentration of each
corresponding pair (x axis).
The QQ plot or quantile quantile plot is a
graphical technique for determining if two
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 CHAPTER 11 – SAMPLING, analysis and quality control
Figure 11.1.5
Box and whisker plot comparing copper results for
primary and external check lab.
data sets come from the same population.
The quantiles of the first data set (primary
laboratory) are plotted against the quantiles
of the second data set (check laboratory). If
the two sets come from a population with
the same distribution, the points should fall
approximately along a 45 degree reference line.
Departures from this distribution are indicative
of measurement error.
The advantages of the QQ plot are:
•• the samples from the check laboratory do
not need to be paired with samples from
the primary laboratory and the number of
samples from each laboratory do not need to
be equal; and
•• many distributional aspects can be
simultaneously tested: shifts in location,
shifts in scale, changes in symmetry and the
presence of outliers.
11.2. BEST ANALYTICAL METHODS
FOR COMMON METALS/ hydrofluoric, nitric, perchloric and hydrochloric
MINERALS/COMPOUNDS
Most analytical instrumentation require samples
to be decomposed in one form or another
before samples can be read and concentrations
determined. A variety of digestion methods are
commonly used.
Chapter11.indd 323
Digestion methods
Perchloric acid digestion is an oxidative attack
offering a cost-effective approach for the analysis
of trace elements in soils, sediments and rocks.
It is generally quantitative for base metal sulfides
and oxides but incompletely attacks silicates and
will not dissolve certain resistate minerals (eg
oxides such as chromite and cassiterite). It does
not totally digest the sample and is not suited to
resource quality work.
Aqua regia digestion uses a mixture of
concentrated hydrochloric and nitric acids able
to dissolve gold, sulfides, carbonates and most
oxides. The proportions of these acids vary
between laboratories, as does the temperature
of the digestion, resulting in variable degrees of
decomposition. Aqua regia digestion has limited
effect on barite, cassiterite, chromite, gahnite,
garnet, ilmenite, monazite, rutile, sphene and
zircon. Silicates are only slightly to moderately
attacked, depending on the mineral and the
degree to which it is altered. If gold is important,
larger sample sizes should be used to reduce the
sampling error.
Aqua regia is a useful exploration tool and the
method of choice for many grassroots exploration
programs, as low levels of detection are possible
for multi-element suites, including gold. The low
detection levels are achievable due to the low
dilution factors and low total dissolved salts. As
with the perchloric acid leach it is not generally
used for resource quality work, even though,
where base metals are incorporated exclusively
in sulfides, oxides and carbonates, extraction is
almost quantitative.
Three acid digestion uses a mixture of
nitric, perchloric and hydrochloric acids. It is
less common than aqua regia and four acid
digestions and is not available at all commercial
laboratories. It is the method of choice for grade
control at many copper operations, particularly
in South America.
Four acid digestion, often referred to as
mixed acid digestion (MAD), total acid digestion
(TAD) or strong acid digestion, uses a mixture of
acids. It is the most potent acid attack in
geochemistry and approaches a total acid digest
for most mineral species. It is particularly well
suited to the analysis of base metal ores. The use
of hydrofluoric acid achieves the breakdown of
most silicates, however, some elements (Si, As,
Sb, Cr, U and Au) may be erratically volatilised
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 CHAPTER 11 – SAMPLING, analysis and quality control
depending on digestion conditions, and certain
mineral species may not be totally dissolved
or may not go into solution (eg zircon, sphene,
magnetite, barite, gahnite, chromite and
cassiterite). Whilst major elements (excluding
Si) can be determined by this method, fusion
techniques are preferable.
Four acid digestion is useful for many
applications, including exploration using multi-
element suites. The digestion can be optimised
for higher grade material, where it is particularly
well suited to the analysis of base metal ores.
Other acid digestions exist for specific
applications, such as the determination of
mercury and soluble copper.
Sodium peroxide fusion provides total
decomposition of the sample and is therefore
well suited to samples containing minerals of
interest that are resistant to acid attack. These
include minerals containing rare earth elements
(REE), high field strength elements (HFSE), Sn,
W, Ti and V. Following fusion at 700°C in nickel,
zirconium or alumina crucibles the fusion cake
is leached with hydrochloric acid, diluted with
distilled water and elements measured by ICP-
OES or ICP-MS (inductively coupled plasma
mass spectrometry). Disadvantages of the
method are:
•• the potential loss of volatiles on fusion;
•• elevation of detection limits compared with
acid digest methods – this is due to the
greater levels of dilution required to offset
the high salt levels in solution that may affect
instruments such as ICP-MS; and
•• contaminants from the flux and crucibles
(eg Na and Ni, Cr, Cu, Mn, Zn, Zr, Hf and Al,
depending on the crucible type).
Lithium borate fusion is used to prepare a wide
range of silicate rocks and ores for analysis by
X-ray fluorescence, inductively-coupled plasma
optical emission, inductively-coupled plasma
mass spectrometry and atomic absorption.
Samples are combined with a mixture of lithium
metaborate and lithium tetraborate fluxes and
fused in platinum crucibles at temperatures
between 900°C to 1250°C. The resultant glass
can be either formed into a disc and presented
to an XRF instrument for direct analysis or
dissolved in dilute acid for measurement by ICP-
OES, ICP-MS or AAS. As with sodium peroxide
fusion refractory minerals and major oxides,
including SiO2, are readily dissolved. High
sulfide bearing rocks may require pre-roasting of
the sulfides prior to fusion to prevent attack on
324 Field Geologists’ Manual
Chapter11.indd 324
the expensive platinum ware or the addition of
an oxidant to the flux.
Other fusions such as oxidative alkaline
fusions are used for specific applications such as
in the determination of barium, strontium and
fluoride.
Fire assay – see section headed ‘Gold’.
Reading methods
A variety of reading methods are available
for quantifying the concentration of elements
in geological materials. Each method has
its strengths and weaknesses and the most
appropriate instrumentation will depend on the
target elements, concentration ranges, possible
interferences and chemical and mineralogical
composition of the samples. A periodic table
of recommended reading methods for the
commonly measured elements is presented in
Figure 11.2.1. The selection of which method
or methods to use should be made in close
consultation with laboratory personnel.
Atomic absorption spectrometry (AAS) is
a spectroanalytical procedure for the deter-
mination of the concentration of elements
based on absorption of light by free atoms in
the gaseous state. The modern form of AAS was
developed in the 1950s and is still regarded today
as a valuable tool in modern geochemistry. Its
main applications in today’s mineral industry are
for the determination of gold and base metals.
It is cost effective where the number of elements
of interest are limited to one to four and is the
finish of choice at many commercial labs for over
range (>1 per cent) base metals. Low detection
limits for gold can be obtained using graphite
furnace AAS.
Inductively coupled plasma optical emission
spectrometry (ICP-OES) also referred to as
inductively coupled plasma atomic emission
spectrometry (ICP-AES) is a form of emission
spectroscopy using an inductively coupled
plasma to produce excited atoms and ions that
emit electromagnetic radiation at wavelengths
characteristic of a particular element. The
intensity of this emission is proportional to the
concentration of the element in the sample.
Compared with AAS, ICP-OES and ICP-MS are
modern techniques that have revolutionised
the geochemical study of geological samples.
The main advantage of ICP-OES is the ability
to rapidly and simultaneously determine multi-
element suites that can be tailored to the various
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Chapter11.indd 325

Figure 11.2.1
Best analytical methods for common minerals/metals/compounds1.

CHAPTER 11 – SAMPLING, analysis and quality control

Field Geologists’ Manual

1. Modified from Intertek Genalysis Laboratories, with permission.

27/07/2011 5:54:20 PM

325
 CHAPTER 11 – SAMPLING, analysis and quality control
commodities. Major and minor elements and
some trace elements can be determined by ICP-
OES. It does not have the sensitivity of ICP-MS
for many elements.
Inductively coupled plasma mass spectro-
metry (ICP-MS) is based on coupling together
an inductively coupled plasma as a method
of producing ions (ionisation) with a mass
spectrometer as a method of separating and
detecting the ions. It has superior sensitivity to
ICP-OES and can be used to complement the
latter by extending the lower limit of detection
to well below the element concentration ranges
commonly encountered in unmineralised
rocks and soils. With appropriate dilutions and
calibration controls, high levels can be analysed
too. The two finishes, ICP-OES and ICP-MS,
are frequently combined using the same digest
solution, thus providing an extremely powerful
analytical tool for the determination of major,
minor and trace elements.
X-ray fluorescence spectrometry (XRF) is
based on the emission of secondary (fluorescent)
X-rays from elements in a glass disc that have
been excited by bombardment with high energy
X-rays or gamma rays. The glass disc is prepared
by fusion of a rock sample in a lithium borate
flux, pouring into a mould and quenching into a
disc-shaped glass. The method has been in use
for many decades and it remains the preferred
method for the analysis of major element
oxides in silicate rocks. For a time following the
advent of ICP technology, XRF was somewhat
overshadowed, but with recent improvements in
instrumentation and automation of disc making
it has undergone a resurgence in popularity.
Today XRF is the method of choice in whole rock
major element analysis, in particular iron and
nickel laterite ores and increasingly, base metal
sulfide ores. It is capable of a very high degree of
accuracy and precision.
Classical methods
With the exception of gold, classical methods,
sometimes referred to as ‘wet chem’ methods,
are generally reserved for the analysis of very
high grade ores and concentrates. They are
expensive methods and have elevated detection
levels appropriate to materials with high metal
concentrations. Broadly they can be divided into
gravimetric methods (eg electro-gravimetric
determination of copper, determination of Zn by
dimethylglyoxime precipitation) and titrimetric
methods (eg short iodide titration for copper).
326 Field Geologists’ Manual
Chapter11.indd 326
They are extremely accurate methods and
therefore used extensively in umpire analysis of
shipping concentrates.
A classical method is frequently used for
the determination of gold in high grade ores.
This entails conventional fire assay with gold
recovered from the silver prill by parting
(dissolution of the silver in nitric acid) and
weighing. At many commercial laboratories it
is the default method at concentrations above
10 ppm while some offer it as an option at grades
as low as 3 - 4 ppm Au.
Non-destructive methods
These are methods where elements are
determined directly on an intact sample, that
is without prior decomposition of the sample.
Generally samples are presented for analysis
in powder form to achieve a homogeneous and
representative sample.
Pressed powder X-ray fluorescence is a low-
cost, rapid turnaround technique for the analysis
of trace to minor quantities of single elements.
The pulverised sample is mixed with a binder and
pressed into a briquette under a press. It is well
suited to elements held in refractory minerals
that pose difficulties for acid digest methods in
particular. Consistent particle size distribution is
essential to minimise errors due to mineralogical
and particle size effects. Matrix matched controls
are important when rapid matrix correction
routines are used. It is not considered suitable
for resource evaluation or lighter major elements
although it is in limited use in robotic mine
laboratories for grade control.
Instrumental neutron activation analysis
(INAA) is not widely used due to the scarcity
of nuclear reactor facilities; however, it can be
a powerful and effective form of analysis for
modest batch sizes. The technique involves
bombarding the sample with neutrons in a
reactor and measuring the induced gamma-
ray activity at various wavelengths unique to
the particular elements being measured. It is a
highly precise method particularly suited to Au,
REE and U. Elements that can be determined by
this method include Ag, As, Au, Ba, Br, Ca, Cd,
Ce, Co, Cr, Cs, Eu, Fe, Hg, Ho, Hf, Ir, K, La, Lu,
Mo, Na, Nd, Ni, Rb, Sb, Sc, Se, Sm, Sn, Sr, Ta, Tb,
Te, Th, U, W, Yb, Zn and Zr.
Gold
A variety of methods are available for the
determination of gold owing to its wide
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 CHAPTER 11 – SAMPLING, analysis and quality control
concentration range from less than one part per
billion (ppb) in barren soils, sediments and rocks
to in excess of 20 000 ppb (20 ppm or g/t) in
high grade ores. In addition, the distribution of
gold in geological samples can be sporadic and
cause severe sampling problems. Conventional
lead collection fire assay remains the generally
preferred method, however, aqua regia digestion
and cyanide leach methods are useful options for
particular applications.
Fire assay involves the firing of a 25 - 50 g
sample in the presence of a borax, soda ash,
litharge (Pb oxide), baking flour, trace silver
and other additives (dependent on sample
composition) in a crucible or fire assay pot.
For difficult matrices (including concentrates)
special fluxes and/or a reduced charge weight as
low as 5 g may be used. During the firing process
the lead oxide is reduced to molten lead which
quantitatively scavenges the gold (+ Pt and Pd)
and silver from the silicate melt. As the molten
lead is considerably heavier than the silicate
melt, it collects at the bottom of the crucible.
The molten lead (and slag) is poured from the
crucible into a mould where the lead forms a
button which can be readily separated from the
adhering slag. The lead button is then placed in
a cupel made from magnesia. In the cupellation
process the lead and other base metal impurities
are oxidised and absorbed into the cupel leaving
behind a silver prill into which the gold has
quantitatively segregated. The prill is treated with
nitric acid to remove the silver. The gold residue
is either weighed directly (gravimetric finish) or
dissolved in aqua regia and diluted for reading by
AAS, ICP-OES or ICP-MS (instrumental finish).
For low level gold, where a 1 - 2 ppb detection
level is required, methods such as graphite
furnace AAS, solvent extraction flame AAS,
ICP-OES or ICP-MS are employed. For ore
grade samples relevant to resource definition
and grade control, a 10 ppb detection level is
generally acceptable and flame AAS or ICP-OES
is used. For sulfide-rich ores a pre-roast step
may be included prior to firing to oxidise the
sulfides. Platinum and palladium can also be
quantitatively determined by lead collection fire
assay with ICP-OES (5 ppb detection) or ICP-MS
(1 ppb detection) instrumental finish.
Screen fire assay is typically used for the
analysis of samples containing coarse gold and
where a typical 50 g fire assay would be subject
to unacceptably large sampling errors. A 1 kg
representative pulverised split is screened
Chapter11.indd 327
generally at 100 or 150 microns using a cloth
screen. The entire oversize fraction along with
the cloth screen is analysed by fire assay to
determine the coarse gold component while the
undersize fraction is analysed in duplicate by
routine fire assay to determine the non-coarse
gold component. A weighted average is then
calculated to determine the overall gold content
of the original 1 kg sample. The sample should
not be pulverised too finely as some gold may
plate out on the mill and be lost.
Aqua regia gold determinations are mainly
used for grassroots exploration and are in most
instances inappropriate for resource definition.
Although this digest is incomplete for silicates
and refractory minerals, many elements, in
particular base metals and many pathfinder
elements, can be determined simultaneously
with gold. The choice of reading method is
dependent on the expected grade range with
the same criteria used for fire assay applicable.
Where gold is occluded in silicates recoveries
may be compromised.
Cyanide leaches are used to extract cyanide
soluble gold from large samples (up to 5 kg) for
both low level and high grade gold analysis.
For very low level work, such as grassroots
exploration, bulk leach extractable gold (BLEG)
analysis is typically performed on screened
stream sediment samples. Detection limits of
0.01 ppb are achievable by this method and
allow detection of anomalies in the 5 - 20 ppb
range or lower in regional surveys. This method
can accurately reproduce ppb gold anomalies in
calcrete, for example.
The large sample size permitted by cyanide
leaching is ideally suited to the evaluation of
nuggety ores where the presence of coarse gold
produces highly variable results on conventional
fire assay charge weights (25 - 50 g). Extended
grinding times for nuggety ores will generally not
overcome the nugget effect but result in plating
out of gold on the mill. It should be noted that
extraction efficiencies by cyanide leach are less
than total (typically around 90 per cent) and
mimic those achieved in carbon in leach (CIL)
and carbon in pulp (CIP) plants. Cyanide in
excess of 0.02 per cent dissolves gold at a rate of
3.36 μg/h, so a typical 24 hour cyanide leach will
dissolve a gold particle up to 80 µm in diameter.
Recoveries can be determined by fire assay
analysis of the leach residue.
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 CHAPTER 11 – SAMPLING, analysis and quality control
The LeachWELL™ accelerated cyanide leach
process is frequently used for high-grade ores.
This can dissolve gold at a rate of 50 times that
of normal BLEG.
Base metals
The chief commodity base metals copper, nickel,
zinc and lead occur in measurable concentrations
in all geological materials. For low level
reconnaissance evaluation of stream sediment
and soil samples or lightly mineralised rock
samples acid digest ICP-OES or AAS analysis
are the preferred methods. The accuracy of these
‘geochem’ methods is generally ±10 per cent and
considered fit for purpose. If gold, platinum or
palladium are required then an aqua regia digest,
preferably on a larger sample, and with an ICP-
MS finish is recommended.
Base metal sulfide or oxide ores, where
expected metal concentrations exceed 0.5 to
one per cent, often require methods with greater
accuracy (±5 per cent) and precision. Acceptable
methods for resource definition or grade control
work are ore grade four acid digest ICP-OES
or AAS, sodium peroxide fusion ICP-OES and
lithium borate fusion XRF.
Iron ores
Whole rock major element analysis of iron
ores requires a fusion process to obtain total
element abundances. Samples are dried at 105°C
and analysed using lithium borate fusion XRF,
or lithium borate or sodium peroxide fusion
ICP-OES. Because of its superior accuracy and
precision XRF is widely regarded as the preferred
method. Loss on ignition (LOI) is determined
on a separate aliquot of the dried sample and
measures weight loss between 105°C and 1000°C
due to volatilisation of structural OH- molecules
from hydrous minerals (goethite, limonite, clays,
micas, amphiboles, etc), CO2 from carbonates
and SO2 from sulfides, which, in turn, oxidise.
For magnetite ores where ferrous iron (Fe2+) is
substantial, a gain in weight may be recorded
due to the uptake of oxygen accompanying the
conversion of Fe2+ to Fe3+. In such instances the
weight increase associated with oxygen uptake
is greater than the combined effects of volatile
losses.
Some ores are highly hygroscopic and
rehydration following drying can be problematic.
Dried samples should be cooled in a desiccator
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Chapter11.indd 328
prior to weighing for analysis. The alternative
treatment is to allow samples to equilibrate to
the laboratory atmosphere, weigh for analysis,
determine moisture on a separate aliquot and
then correct results to a dry basis.
Ferrous iron determination is important for
magnetite ores, where a significant component of
iron is present in the divalent state. The sample
is dissolved in acid and ferrous iron determined
volumetrically by titration.
Davis Tube recovery (DTR) simulates plant
recoveries of ferromagnetic concentrates using
a Davis Tube. Recoveries of ferromagnetic
constituents can be assessed through control of
magnetic field strength and sample particle size.
The chemical compositions of both the magnetic
and non-magnetic fractions are analysed by XRF.
Nickel laterite ores
The major element analytical methods used for
nickel laterite ores are the same as those for iron
ores. Nickel laterites can be highly hygroscopic
(more so than some desiccants) so extreme
care should be taken during the drying stage.
Incomplete drying of samples or re-absorption of
moisture following drying can be major sources
of error in the analysis of these materials. For
this reason the alternative treatment described
above for iron ores should be considered where
ores are known to be hygroscopic. As with iron
ores, lithium borate fusion XRF is the preferred
method, but lithium borate or sodium peroxide
fusion ICP-OES are also acceptable. Where the
full major element suite is not required four acid
digest ICP-OES will give total concentrations for
nickel and cobalt comparable to fusion methods.
Uranium
For exploration applications involving analysis
of soils and sediments free of resistate minerals,
an aqua regia digest followed by ICP-MS is
suitable, particularly if gold is also required.
Pressed powder pellet XRF also provides a rapid,
cost-effective method of analysis for grassroots
exploration. Higher grade uranium can be
determined by ore grade four acid digestion
and ICP-MS analysis or by fusion techniques.
Although uranium is remarkably soluble by this
digestion in resistate minerals such as davidite,
apatite, zircon, monazite and sphene, other
constituents are incompletely digested. For this
reason fusion techniques are recommended
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 CHAPTER 11 – SAMPLING, analysis and quality control
for refractory minerals likely to host uranium.
Lithium borate fusion with XRF or ICP-MS
finish or sodium peroxide fusion ICP-MS are the
preferred methods.
In summary, depending on compositional
matrices, the following methods are suitable for
the grade ranges indicated:
•• geochem aqua regia or four acid digest ICP-
MS: 0.01 ppm to one per cent U,
•• pressed pellet XRF: 5 ppm to one per cent,
•• ore grade four acid digest ICP-MS: 0.5 ppm
to >30 per cent,
•• delayed neutron counting: 0.1 ppm to one per
cent,
•• lithium borate fusion ICP-MS: 0.5 ppm to
>30 per cent,
•• sodium peroxide fusion ICP-MS: 0.5 ppm to
>60 per cent,
•• lithium borate fusion XRF: 10 ppm to >60 per
cent, and
•• instrumental neutron activation analysis:
0.5 to 50 per cent.
Rare earth elements (REE) and high
field strength elements (HFSE)
Lithium borate fusion ICP-MS is the best
method for the analysis of REE and HFSE (Y,
Zr, Hf, Nb, Ta, Th, U) as the host minerals are
commonly refractory and the heavy REE not
completely attacked by acid digestion. Sodium
peroxide fusion ICP-MS will also provide total
concentrations but detection levels are elevated
compared with borate fusion. It is important
that samples are finely ground (95 per cent
minus 75 micron) to ensure complete fusion of
refractory phases.
Platinum group elements (PGE)
The conventional lead collection fire assay
method is capable of quantitatively recovering
platinum and palladium in addition to gold. For
all six PGE (Pt, Pd, Ru, Rh, Ir and Os) nickel
sulfide (NiS) is used as the collector in place of
lead. The PGEs have a very high partitioning
coefficient into a NiS melt relative to a silicate
melt and are consequently quantitatively
scavenged into the NiS phase. Gold may not
be completely partitioned into the NiS. Unlike
lead collection fire assay, the molten material is
allowed to cool in the pot before the pot is broken
Chapter11.indd 329
open and the NiS button recovered from the slag.
There is no cupellation stage. The NiS button is
simply pulverised and a portion of it digested in
hydrochloric acid. The nickel sulfide is dissolved
leaving a residue of insoluble PGE sulfides which
are dissolved in aqua regia and then analysed
by ICP-MS or, if grades are sufficiently high
(>10  ppb), by ICP-OES. The insoluble PGE
sulfides can be analysed directly by INAA, but
with poorer sensitivity than ICP-MS.
It should be noted that nickel sulfide collection
fire assay is a highly specialised method and not
widely available.
Partial selective leach
Mobile metal ions and related pathfinder
elements associated with orebodies can be
mobilised in groundwaters and migrate upwards
to be fixed in surficial soils and sediments. Partial,
selective or sequential leach geochemistry
extracts these loosely bound ions from the
soil and sediment media and provides an
enhanced geochemical response to underlying
mineralisation. Conventional strong acid
digestions are less selective than partial leaches
and in mature terrains the bulk chemical
signature of deep overburden may mask the
presence of these subtle anomalies.
There are a range of partial leaches available
that vary in their ability to selectively and
sequentially dissolve specific components of
the sample. They are analogous to leaches
used for agricultural and environmental
purposes, although many of the methods used
in geochemical exploration are proprietary or
licensed to commercial laboratories. Examples
of the more widely available leaches include
water, ammonium acetate, ionic, cold and hot
hydroxylamine hydrochloride and sodium
pyrophosphate leaches. Consultation with the
laboratories is highly recommended to optimise
sampling protocols and digest requirements. An
orientation study is also valuable. Leaches are
generally done on screened samples that have
not been pulverised.
Water – a leach using demineralised water for
extracting the water-soluble component.
Ammonium acetate – a buffered leach to
extract exchangeable cations adsorbed by clay
and elements co-precipitated with carbonates.
It is a very weak leach targeting the most weakly
bound ions and often used in sequential leaches
prior to more aggressive leaches.
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 CHAPTER 11 – SAMPLING, analysis and quality control
Ionic – a buffered sodium cyanide leach
targeting ions weakly bound to the surface of
particles in regolith or soil.
Cold hydroxylamine hydrochloride – this
widely used leach is selective for manganese
oxides which are powerful scavengers of specific
heavy metals. Manganese occurs as oxides and
hydroxides in several oxidation states and in
various amorphous and crystalline forms having
an extremely high cation exchange capacity.
These compounds are therefore very efficient
scavengers of many trace elements. The leach
will not attack crystalline iron oxides, but will
dissolve very small amounts of amorphous
hydrous iron oxide.
Hot hydroxylamine hydrochloride – a leach
combining higher hydroxylamine concentration
and elevated temperature and capable of
dissolving amorphous hydrous iron hydroxide
and crystalline manganese hydroxide while
leaving crystalline iron oxide substantially intact.
Amorphous iron hydroxides are more powerful
scavengers of mobile metal ions than crystalline
forms of iron oxide.
Sodium pyrophosphate – this leach specifically
targets metals forming chelation complexes with
the humus component of soils and sediments. It
will not attack sulfides nor dissolve significant
amounts of amorphous iron oxides. Variations in
the concentrations of organically-bound metals
such as copper, zinc, cobalt, nickel, iron and
aluminium have been shown to provide good
anomaly contrast.
Hydrogeochemistry
The chemical analysis of ground waters can be
a valuable adjunct to exploration programs.
Trace elements in ground waters are generally
present at extremely low levels. Special
handling and storage procedures are needed
for the preservation of samples. Waters can
be analysed directly with ICP-MS and with the
dramatic improvements in sensitivity of ICP-
330 Field Geologists’ Manual
Chapter11.indd 330
MS instruments incorporating electro thermal
vaporisation technology, gold can now be directly
determined in groundwaters to a detection limit
of 0.5 parts per trillion. Brines may have to be
diluted before analysis, with some degradation
of sensitivity as a consequence. Being a more
homogeneous medium, a water sample will be
more representative of the water body than a
rock sample will be of the surrounding bedrock.
Large areas can be explored with relatively few
samples, potentially providing a cost-effective
exploration tool.
Biogeochemistry
Biogeochemistry, or phytogeochemistry, uses
living plant tissue as the medium for exploration.
Plants scavenge elements and translocate them
to foliage, twigs, bark, flowers and seeds making
them efficient geochemical samplers, able to
integrate material from a much wider area than
the equivalent single soil sample. Foliage and
bark generally give the strongest geochemical
signature. Samples are easy and cheap to collect
and, compared with conventional forms of
geochemical exploration, environmental impact
is minimal. Analysis of plant tissue provides
information on the underlying geology and can
be particularly effective in areas of transported
cover or regolith-dominated terrain.
Trace element levels in plants are generally
much lower than in soils and consultation with
the laboratory regarding sampling protocols
to minimise contamination is recommended.
An orientation study is advisable to determine
the most appropriate species too collect and
which tissue type works best. Samples are dried,
milled in specialised equipment and digested
in a modified aqua regia solution. Analysis
by combined ICP-OES and ICP-MS provides
multi-element suites that are the most useful for
interpreting biogeochemical data.
Samples may be ashed prior to digestion to
enhance sensitivity for some applications.
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 CHAPTER 11 – SAMPLING, analysis and quality control

11.3. GENERAL PREFERRED SAMPLE MASS NOMOGRAM1

Maximum ore mineral particle diameter in mm

1. From Gy, P, 1956. Nomogramme d’Echantillonnage (Societe de Minerais et Metaux: Paris).

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 CHAPTER 11 – SAMPLING, analysis and quality control

11.4. GRAPHS OF PARTICLE SIZE AND PREFERRED SAMPLE MASS FOR

GOLD ASSAYS1
Figure 11.4.1
Relationship between number of particles per 1 kg sample, particle mass (assuming all particles to be of
uniform mass), and grade or tenor of the sample in parts per million. Scales to right relate grain size of
gold spheres and flakes to particle mass.

1. From Clifton, H E, Hunter, R E, Swanson, F J and Phillips, R L, 1969. Sample size and meaningful gold analysis,
USGS prof paper 625-C.

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CHAPTER 11 – SAMPLING, analysis and quality control

Figure 11.4.2
Size of sample required to contain an expected 20 particles of gold as a function of the combination of gold
particle size and grade, assuming all gold particles to be of uniform size and randomly distributed in the deposit.

Size of sample required to contain an expected 20 particles of gold as a function of the combination of gold particle size and
grade, assuming all gold particles to be of uniform size and randomly distributed in the deposit.

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