Exploration and Mining Geology, Vol. 17, Nos. 34, p.

131144, 2008
2009 Canadian Institute of Mining, Metallurgy and Petroleum.
All rights reserved. Printed in Canada.
0964-1823/00 $17.00 + .00

Quality Control of Assay Data: A Review of Procedures for

Measuring and Monitoring Precision and Accuracy
M. Abzalov1,*,
(Received August 30, 2007; accepted September 9, 2008)

Abstract Control of analytical data quality is usually referred to in the mining industry as Quality As-
surance and Quality Control (QAQC), and involves the monitoring of sample quality and quantification
of analytical accuracy and precision. QAQC procedures normally involve using sample duplicates and
specially prepared standards whose grade is known. Numerous case studies indicate that reliable control
of sample precision is achieved by using approximately 5% to 10% of field duplicates and 3% to 5% of
pulp duplicates. These duplicate samples should be prepared and analyzed in the primary laboratory.
Bias in the analytical results can be identified by inclusion of 3% to 5% of the standard in each sample
batch. Several different standards are used, with values spanning the practical range of grades in the actual
samples. A blank (a sample in which the concentration of metal of interest is below detection limit) should
also be included. Standard samples alone cannot identify biases introduced during sample preparation, and
therefore approximately 5% of the duplicate samples (coarse rejects and pulp) should be processed and
assayed at another, external, reputable laboratory.
This paper discusses techniques used for estimation of errors in precision and accuracy, and over-
views diagnostic tools. It is shown that one of the most commonly used methods, the Thompson-Howarth
technique, produces consistently lower results than other methods. These results reflect the nature of this
method, which relies on the assumption of a normally distributed error, and thus produces biased results
when errors have a skewed distribution. This study concurs with the suggestion of Stanley and Lawie
(2007: Exploration and Mining Geology, v. 16, p. 265274) to use the average coefficient of variation
(CVAVR(%)) as the universal measure of relative precision error in mine geology applications:

2 N (a - b )2
i
CVAVR (%) = 100
N
(a + b )
i
2
i =1 i i

Based on case studies, an acceptable level of sample precision is proposed for several different deposit
types. 2009 Canadian Institute of Mining, Metallurgy and Petroleum. All rights reserved.

Key Words: Mining geology, QAQC, duplicates, standards.

Sommaire Le contrle de la qualit des donnes analytiques est habituellement dsign sous lap-
pellation dAssurance et Contrle de la Qualit (ACQ), elle implique le suivi de la qualit des chan-
tillons et la quantification de la reproductibilit et la prcision analytiques. Les procdures des pro-
grammes dACQ impliquent habituellement lusage de duplicata et de standards analytiques dont
la teneur est connue. Plusieurs tudes de cas indiquent quune bonne fiabilit du contrle de la prci-
sion des chantillons est atteinte par lusage de 5% 10% de doublons sur le terrain et de 3% 5%
de doublons de pulpe. Ces duplicata devraient tre prpars et analyss au laboratoire principal.
Un biais des rsultats analytiques peut tre identifi par linclusion de 3% 5% dchantillons standard
dans chaque envoi dchantillons. Plusieurs standards sont utiliss, avec des valeurs couvrant ltendue
des teneurs habituellement rencontres dans des chantillons rels. Un blanc (un chantillon dans lequel la
concentration dun mtal donn est sous la limite de dtection) devrait aussi tre inclus. Lemploi exclusif
dchantillons standards ne permet pas lidentification de biais rsultant de la prparation des chantillons,
de telle sorte quenviron 5% des duplicata (rejets grossiers et pulpes) devrait tre traits a un autre labo-
ratoire indpendant et fiable.
Cet article passe en revue les techniques utilises pour valuer lerreur lie la prcision et a la repro-
ductibilit, et effectue aussi un survol de divers outils diagnostiques. Il ressort de cet examen quune des

1
MASSA Geoservices, Mt. Claremont, Western Australia, Australia WA6010.
* Present address: Rio Tinto Exploration, PO Box 175, Western Australia, Australia WA6984.

Corresponding Author: E-mail: marat.abzalov@riotinto.com

132 Exploration and Mining Geology, Vol. 17, Nos. 34, p. 131144, 2008

techniques les plus frquemment utilises, la mthode Thompson-Howarth, fournit des estims systmati-
quement infrieurs ceux provenant des autres mthodes. Ces rsultats sont un reflet de la nature de cette
mthode, laquelle assume une distribution normale de lerreur, biaisant ainsi les rsultats lorsque lerreur
prsente une distribution asymtrique. La prsente tude recommande de privilgier lusage du coefficient
moyen de variation (CVAVR(%)) en tant que mesure universelle de la prcision relative de lerreur dans les
applications minires tel que suggr par Stanley and Lawie (2007: Exploration and Mining Geology, v.
16, p. 265274):
2 N (a - b )2
i
CVAVR (%) = 100
N
(a + b )
i
2
i =1 i i

Appalaches du nord. Les gtes aux environs de Clarence Stream dans le sud-ouest du Nouveau
Brunswick sont un exemple de ce type de gisement, mettant en valeur ce qui pourrait devenir un district
aurifre majeur dans la rgion. 2009 Canadian Institute of Mining, Metallurgy and Petroleum. All
rights reserved.

Introduction ple can be a second blast-hole sample collected from the

The quality of geochemical data used in mineral ex-
ploration and development is determined and reported in
terms of precision and accuracy (JORC, 2004). Precision,
or repeatability, is a measure of how close replicate sample
values are to each other, whereas accuracy is a measure of
how close the values are to the true grade. The procedures
involved in monitoring precision and accuracy are referred
to as Quality Assurance and Quality Control (QAQC).
Despite unanimous recognition of the importance of
QAQC in the minerals industry, no uniform, industry-wide
procedures have been established, and the methods used
vary significantly in complexity and effectiveness. Given
the growing need in the mining and exploration industry
for development of a standardized approach to quantify-
ing the quality of assay values, it is important to compare
the currently used QAQC techniques. Such a comparative
analysis will assist in developing standardized QAQC pro-
cedures, which, in turn, will facilitate assessment of the
technical merits of a mining project.
This paper discusses techniques used in the mining in-
dustry for monitoring precision and accuracy of geochem-
ical analyses of samples, with a particular emphasis on
the statistical methods used for QAQC data analysis. The
most common estimators of precision errors are compared
by applying them to the same data sets, which have been
collected from operating mines and mining projects and
which represent different commodities and mineraliza-
tion styles. In order to facilitate statistical analysis of the
QAQC data, Visual Basic codes have been developed in
an Excel spreadsheet (AMZ_QAQC.xls), which can be ob-
tained from the author upon request.
Principles of Sample Quality Control
Precision
Analytical precision is normally monitored by using
paired analyses. The first sample is referred to as the ori-
ginal sample, and the second is called the duplicate. A
duplicate sample is merely another sample collected from
the same place following the same rules as used for col-
lecting the original sample. In practice, the duplicate sam-
same blast-hole cone, or another split (e.g., quarter) of the
drill core. It also can be a duplicate sample collected at a
particular stage of the sampling protocol. Where the sam-
pling protocol includes several stages of comminution and
subsampling, duplicate samples should be taken at every
subsampling stage.
Duplicate samples are prepared and assayed using the
same procedures that were used for the original samples
and in the same laboratory. Variations of the results be-
tween matching pairs of sample assays, when assayed in
the same laboratory, allow estimation of precision errors
associated with sample preparation and analysis.
Accuracy
Accuracy of analyses is normally monitored by includ-
ing samples with known concentrations of elements (stan-
dards) with each assay batch. Standards are available com-
mercially that have been prepared and assayed rigorously
following appropriate procedures (Kane, 1992), and the
results statistically certified. Best practice is to use stan-
dards from material mineralogically similar to that of the
studied mineralization; these are called the matrix-matched
standards.
Possible contamination during assaying is controlled by
including blanks with the sample batch, which are materi-
als that have very low grades of the metal of interest, usu-
ally below the detection limit of the analytical method to
be used. It is common practice to use barren quartz as the
blank material.
Standards and blanks are called reference materials, and
are used for detecting possible biases in reported analytical
values, and for quantifying the accuracy errors. Leaver et
al. (1997, p. 3) defined a reference material as a substance
for which one or more properties are established suffi-
ciently well to calibrate a chemical analyser or to validate a
measurement process. A reference material is classified as
certified if it was issued and certified by an agency such as
the Canadian Centre for Mineral and Energy Technology
(CANMET), the National Institute of Standards and Tech-
nology (NIST), or other government agencies whose tech-
nical competency is internationally recognized (Leaver et
al., 1997).
 Quality Control of Assay Data: A Review of Procedures for Measuring and Monitoring Precision and Accuracy M. Abzalov 133
An alternative approach to measuring accuracy is to re-
peat the assay of sample duplicates in an external laboratory
that has the authority to act as an independent auditor. This
technique has its strengths and weaknesses. One strength is
that it allows detection of errors introduced at the sample
preparation stage, which commonly cannot be recognized
by use of reference materials in a single laboratory. Un-
like standards, which check for bias only in the analytical
protocol, the independent laboratory check permits the
recognition of bias at various levels of the entire sampling
protocol, depending on the nature of the duplicate material
submitted to the second lab. Of course, if bias is detected,
further analyses must be undertaken (perhaps at a third lab-
oratory) to determine the source of the errors.
QAQC Procedures and Practices
Planning and Implementation of QAQC Programs
Practical recommendations regarding optimal distribu-
tion of QAQC material in analytical batches have been dis-
cussed by many researchers (e.g., Thompson and Howarth,
1978; Valle et al., 1992; Long, 1998; Sketchley, 1998).
Generally accepted rules are summarized below.
Standards (with a range of compositions representative
of the practical range of grades in the actual samples) and
blanks should be inserted in every sample batch in such a
way that they are anonymous to the analyst, and distributed
to allow detection of possible bias in the results.
Duplicate samples should be chosen in such a manner
that significant stages of a sampling protocol are properly
addressed, and the precision errors associated with various
subsampling stages are estimated adequately. Some dupli-
cates should be chosen at random, and others should cover
the entire range of expected grades in the deposit. The
disadvantage of randomly selecting all duplicates is that
such an approach does not lead to adequate representation
of all different grade classes or mineralization types, and
might not assure adequate spatial coverage of the deposit.
Commonly, an excessively large proportion of randomly
collected duplicate samples will be taken from barren or
low-grade material, leaving the higher grade mineraliza-
tion poorly tested.
It is important to ensure that duplicate samples are rep-
resentative for the given deposit, but that at the same time
their distribution maintains, at least partially, the charac-
teristics of being randomly chosen. To meet these two dif-
ferent criteria, the author, based on personal experience,
recommends using the following approach in selecting
duplicate samples. Approximately half of the collected
duplicates should be located by a project geologist with in-
structions to ensure that these duplicates properly represent
the various mineralization styles, grade ranges, and spatial
coverage of the entire deposit. The other half of the dupli-
cates should be chosen at random in each assay batch.
Duplicate samples should be taken at the same time,
and using the same analytical procedures, as the original
samples. It is important that the original samples and their
duplicates are included in the same analytical batch to per-
mit using them for within-batch precision studies. How-
ever, the position of the duplicates within a given analytical
batch should not be immediately sequential to the original
samples, and should also not be systematically related to
them. Numbering of the duplicate samples should disguise
them in the analytical batch.
Frequency of Inserting QAQC Material in Assay Batches
The number of quality control samples and the fre-
quency of their insertion in analytical batches should be
sufficient for systematic monitoring of assay quality. Rec-
ommended quality control materials vary from 5% to 20%
of the total analyses (Garrett, 1969; Taylor, 1987; Valle
et al., 1992; Leaver et al., 1997; Long, 1998; Sketchley,
1998) depending on mineralization type, location of the
mining project, and stage of the project evaluation. A brief
overview of the different recommendations on frequency
of insertion of QAQC materials is given below:
Garrett (1969) recommended that approximately 10% of
geochemical samples should be controlled by collection
of duplicate samples.
Taylor (1987) recommended that from 5% to 10% of
samples analysed by a laboratory should be reference
materials.
Leaver et al. (1997) suggested analyzing one in-house
reference material with every twenty assayed samples,
including at least one certified standard in the same
batch.
Valle et al. (1992) recommended that at least 10% of
the determinations in exploration or mining projects
should be QAQC samples, including standards, blanks,
and duplicates.
Long (1998) suggested that at least 5% of pulps (crushed
and pulverized sample material) should be checked by
an independent laboratory; 5% of field and/or coarse
rejects should have a second pulp prepared and ana-
lyzed by the primary laboratory; and every sample batch
should include from 1% to 5% of standard reference ma-
terials, such as certified standards and blanks.
Sketchley (1998) recommended that every sample batch
submitted to an analytical laboratory should include
from 10% to 15% of quality control samples. In particu-
lar, every batch of 20 samples should include at least one
standard, one blank, and one duplicate sample.
It is a good practice, in addition to using matrix-matched
standard samples, to analyze approximately 5% of the pulp
duplicates and coarse rejects at a reputable external labora-
tory that is authorized to act as independent auditor. Use
of an external laboratory is important because standard
samples alone cannot identify biases introduced at differ-
ent stages of sample preparation within a given labora-
tory. Anonymity of the standards is another issue, because
standards can be easily recognized in the sample batches
and treated more thoroughly by laboratory personnel. The
author believes that assaying duplicate samples (pulp and
coarse rejects) in an external, reputable laboratory should
be routine practice at the feasibility stage of a mining pro-
ject, where accurate data are critical in economic evalua-
tion.
134 Exploration and Mining Geology, Vol. 17, Nos. 34, p. 131144, 2008
Statistical Estimation of Precision Errors
Techniques Based on Analysis of Duplicates
The intuitive approach in assessing paired analytical data
is to plot duplicate sample assays (ai) versus original assays
(bi). Ideally, the paired data representing the independent
assays of the same material should be similar, and should
therefore plot close to line y = x on a binary diagram. In
practice, the values of the paired data are rarely identical
due to sampling and analytical errors, and the data points
will be scattered to a varying degree about the y = x line. If
systematic differences (bias) exist between the original and
duplicate assays, the data might define a more complicated
functional relationships (e.g., y = mx + c). The precision
(error) can be quantified from the paired data through as-
sessing the scatter of the data points, with corrections for
their deviation from the y = x line.
Various methods are available for estimating precision
from the paired data (Garrett, 1969; Thompson and How-
arth, 1973, 1976, 1978; Howarth and Thompson, 1976;
Bumstead, 1984; Shaw, 1997; Francois-Bongarcon, 1998;
Sinclair and Blackwell, 2002; Stanley and Lawie, 2007a).
The most common methods are based on the assumption
of a linear relationship between sampling and analytical
errors, and concentration of the assayed metals (Thompson
and Howarth, 1973, 1976, 1978; Howarth and Thompson,
1976; Bumstead, 1984; Shaw, 1997). Francois-Bongarcon
(1998) has extended this principle to the more complex re-
lationships described by a quadratic model. A special type
of linear model is the Reduced Major Axis model (RMA;
Sinclair and Bentzen, 1998; Davis, 2002; Sinclair and
Blackwell, 2002). This technique is applicable to linear
cases when different sets of paired data exhibit systematic
differences (bias). There have also been attempts (e.g.,
Garrett, 1969) to use geostatistical estimates (variograms)
as a measure of precision. Pitard (1998) suggested a special
diagnostic diagram, the Relative Difference Plot (RDP),
which can be used for detailed analysis of the causes of
poor data precision or sample bias. These methods are re-
viewed below.
Method 1: Thompson-Howarth: The Thomson-Howarth
method was developed in the early 1970s (Thompson
and Howarth, 1973, 1976, 1978; Howarth and Thomp-
son, 1976) and is now widely used in the mining industry.
The method assumes that error is normally distributed,
and that a systematic linear variation in error exists as a
function of sample grade:
Sc = S0 + KC , (1)
where Sc (plotted on the y-axis) is the error measured as
the standard deviation of the duplicates, S0 is the intercept
with the y-axis representing the standard deviation at zero
concentration, K is the slope of the line, and C is the grade
(x-axis). This method assumes no bias (i.e., that the data
follow a normal distribution) and, therefore, must be pre-
ceded by a test for bias.
Relative error (PTH ) at a given grade (C) can be deter-
mined as the precision at one standard deviation confidence
level:
PTH = SC C . (2)
Substituting Sc as defined in Equation 2 into Equation
1 and multiplying by 1001 yields an expression for rela-
tive error of precision (PTH(%)), estimated at one standard
deviation confidence level and expressed as a percentage
of grade (C):
PTH (%) = 100 ( S0 C ) + K , (3)
where the parameters Sc and K have to be deduced empiric-
ally from available data pairs. The relative precision error
(PTH(%)) calculated at the mean grade ( C ) of the studied
samples is given by Equation 4:
N N
a + b
i
i
i
i
C= . (4)
2N
Thompson and Howarth (1973, 1976, 1978) have pro-
posed two approaches for the experimental calculation of
these parameters. The first approach is used when 50 or
more duplicated results are available (Thompson and How-
arth, 1976, 1978). Using N (>50) of the data pairs ai and bi
(i = 1,2,...N), the means of the data pairs (ai + bi)/2 and their
absolute differences |ai bi| are calculated. The data pairs
are sorted in increasing order of their mean grade, and are
subdivided into groups of 11 results. The last group, ac-
cording to Thompson and Howarth (1978, p. 25), should
be ignored if it contains less than 11 records. The average
value of the means for each sample pair, and the median
value of the absolute differences are calculated for each
group of data. Median values are then plotted as a function
of the group means, and a regression line is fitted to the
experimental points (Fig. 1). The slope of the regression
line in Figure 1 represents K, and S0 is the intercept of the
regression line with the y-axis (i.e., at a mean of zero). In
practice, unless N >> 50, fitting regression lines to so few
points commonly leads to peculiar, or even impossible, re-
sults (e.g., a negative intercept with the y-axis).
The Thompson-Howarth method has three constraints:
(1) all measurements must be positive, which is an intrinsic
characteristic of geochemical assays; (2) the slope of the
regression line (K) must be positive; and (3) the intercept
of the regression line with y-axis (S0) must also be positive.
If one or more of these criteria are not met, the method is
not applicable as described.
When the number of duplicate samples is less than 50,
parameters S0 and K cannot be reliably estimated, and
therefore the above method cannot be used to estimate pre-
1
Thompson and Howarth (1973) have used a coefficient of 200 in Equa-
tion 3, which corresponds to precision at 2 standard deviations. In the
current paper, all precision errors are calculated and discussed at 1 stan-
dard deviation confidence level; therefore, in Equation 3, a constant of
100 was used. This change was made in order to avoid confusion when
PTH(%) is compared to other conventional estimates, such as coefficient
of variation (CV(%)) representing relative error at 1 standard devia-
tion.
 Quality Control of Assay Data: A Review of Procedures for Measuring and Monitoring Precision and Accuracy M. Abzalov 135

1 N
si2 2 N (ai - bi ) 2
CVAVR (%) = 100
N
m
i =1
2
= 100
N
(a + b )
i =1
2 . (6)


i i i

Hence, statistics such as AMPD (Equation 7) and HARD

(Equation 8) simply represent the CV(%) multiplied by
constants 2 and 2 , respectively (Stanley and Lawie,
2007a): 2

ai - bi
AMPD = 100 = 2 CV (%) , (7)
(ai + bi ) 2

ai - bi 2
HARD = 100 = CV (%) . (8)
(ai - bi ) 2

Fig. 1. Absolute difference vs. mean of data pairs (for N > 50 data pairs).
Vertical lines separate groups of 11 records. Open squares denote the Stanley and Lawie (2007a) correctly noted that using
experimental points calculated for each group of 11 records. The x-axis such statistics, which are directly proportional to the co-
value of a square corresponds to the average value of the pair means, and efficient of variation, offers no more information than the
the y-axis value corresponds to the median of the absolute differences of CV itself.
the data pairs in a group. The solid bold line is a regression line fitted to
the experimental points. Method 3: Geostatistical Approach: An alternative approach
to estimating the precision of analytical data involves calcu-
cision. To overcome this problem, Thompson and Howarth lation of various geostatistical measures of the spatial cor-
(1978) suggested a second graphical method that infers relation, such as variograms. Garrett (1969) suggested cal-
the approximate value of the relative precision error. This culating precision error between original samples and their
method has limited application in practice because of dif- duplicates by lognormally transforming their assay values,
ficulties in reliably estimating sample precision from such and then applying the formula of the lognormal variogram.
a limited number of data pairs. Consequently, this method This approach has not found wide application in practice.
is not discussed further here. F. Pitard has suggested (pers. commun., 2005) calculat-
2
Method 2: Relative Precision Error (CV, AMPD, HARD): ing relative variance ( s FP ) of the matching pairs of data:
This group of methods includes various estimators based 2
on calculation of the absolute differences between origin-
2
al and duplicate samples, normalized to (divided by) the 1 N ai - bi 2 N a -b
mean grades of corresponding data pairs (Bumstead, 1984; s 2
FP =

2 N i ai + bi
=
N
i ai + bi . (9)
i i
Shaw, 1997; Roden and Smith, 2001; Stanley and Lawrie, 2
2007a). Two of the measurements, Absolute Mean Per-
centage Difference (AMPD) and Half Absolute Relative
Difference (HARD), both described in Table 1, are widely This equation is known in geostatistics as a pair-wise
used in the mining industry. relative variogram (Goovaerts, 1997), and is particularly
useful for variables characterized by strongly skewed sta-
Stanley (2006) has shown that the abso- tistical distributions, and where outliers are present3.
lute difference between paired data is dir- The average precision error can be obtained from Equa-
ectly proportional to the standard deviation tion 9 by taking the square root of the relative variance
( | ai bi = 2 Standard Deviation ), and, consequently, and multiplying by 100 to represent the precision error as a
that the various measurements representing the ratio of the percentage at one standard deviation (Equation 10)4:
absolute differences between paired data to the means of
the corresponding pairs (Table 1) are directly proportional
to the coefficient of variation (CV(%))2:
3
Conventional formula of the pair-wise relative variogram (Goovaerts,
Standard Deviation a - bi 2 . (5) 1997):
CV (%) = 100 = 100 i 1 N
2
Z ( xi ) - Z ( xi + h)
Mean ai + bi

2
g PWR (h) =
Z ( xi ) + Z ( xi + h) ,
2
2N i =1

2
The average coefficient of variation (CVAVR(%)) can be
calculated from N pairs of duplicate samples: where Z(x) is a value of variable (Z) at the location x, and h is a vector
separating Z(x) from Z(xi + h) points.

2
For consistency with other measurements, the coefficient of variation,
CV (one standard deviation divided by mean), is expressed as a percent-
age (CV(%)).
4
When the formula of the pair-wise relative variogram (Equation 9) is
applied to duplicated pairs of samples whose spatial separation is zero
(h = 0), it calculates the PWR(0) value.
136 Exploration and Mining Geology, Vol. 17, Nos. 34, p. 131144, 2008

2 .
PFP (%) = 100 s FP (10) Table 1. Measures of Relative Error Based on Absolute Difference Between Duplicate Data Pairs
Single Duplicate
Error Estimator Pair Formula Reference Comments
Method 4: Partitioning of Total Vari-
ance of Analytical Data: Francois- Also known as Mean Percentage
Absolute Mean ai - bi Difference (MPD; Roden and Smith,
Bongarcon (1998) analysed sampling Percentage Dif- AMPD = 200
and analytical precision by subdividing (ai + bi ) Bumstead 2001) or Absolute Relative Difference
ference (AMPD) (1984) (ARD; Stanley and Lawie, 2007a).
the total precision error variance into
components. The practical recommen- Half Absolute ai - bi
Relative Differ- HARD = 100
dation of that study was to use Equation (ai + bi ) Shaw
ence (HARD) (1997) Half of the corresponding AMPD.
11 for estimating precision variance
if the data represent different grade Notes
classes. Error at one standard devia- ai = original sample; bi = duplicate.
tion is estimated using Equation 12:
(ST (%)), which were recommended by the State Ore Re-
(a - bi ) serves Committee as acceptable precision errors for given
2
s DFB = 2Var i , (11) grade classes (Eremeev et al., 1982). To obtain a reliable
(ai + bi ) estimation of sample precision, it was recommended to
analyze at least 30 data pairs for each grade class (Eremeev
2
PDFB (%) = 100 s DFB . (12) et al., 1982). Where samples have been assayed in the dif-
ferent laboratories, the data are grouped and analysed sep-
Calculation of other components of the global vari- arately for each laboratory.
ance is beyond the scope of the current review and can be
found in the abovementioned paper of Francois-Bongarcon Method 6: Reduced Major Axis (RMA): The Reduced
(1998). Major Axis (RMA) method is a linear regression tech-
nique that takes into account errors in two variables,
Method 5: Precision Estimation Technique Used by Rus- the original samples and their duplicates (Sinclair and
sian GeologistsInternal Quality Control: An approach Bentzen, 1998; Davis, 2002; Sinclair and Blackwell,
developed in the former USSR (Eremeev et al., 1982) 2002). This technique minimizes the product of the devi-
groups data by grade class, and calculates precision er- ations in both the x and y directions, which, in effect,
rors (SR(%)) separately for each class. The precision error minimizes the sum of the areas of the triangles formed
is calculated as a ratio of the standard deviation (S) of the by the observations and a fitted linear function (Fig. 2).
duplicated data to the mean of the data pairs ( C ; Equation The general form of the RMA is
4) in a given grade class (Equation 13):
b = W0 + W1a S RMA , (14)
N

i (ai - bi ) 2 N
2
where ai and bi are matching pairs of data plotted on the
S
S R (%) = 100 = 100 , (13) x- and y-axes, respectively, W0 is the y-axis intercept of the
C N N RMA linear model, W1 is the slope of the model relative
a + b 2 N

i
i i i to the x-axis, and SRMA is the standard deviation of the data
points around the RMA line. The slope of the RMA line
where N is number of sample pairs, and ai is the original (W1) is estimated as the ratio of standard deviations (SD) of
and bi the duplicate of the ith sample pair. It is noteworthy the values ai and bi:
that Equation 13 is the square root of the relative variogram
SD (bi )
applied to the duplicated samples, expressed as percent- W1 = . (15)
age5. SD (ai )
The approach used in Russia and some CIS countries
includes comparison of the precision errors (SR (%)) The intercept of the RMA model with the y-axis (W0) is
calculated in Equation 13 with the theoretical values estimated from

W0 = Mean (bi ) -W1Mean (ai ) . (16)

5
The conventional formula for the relative variogram is as follows (Goo-
vaerts, 1997): The RMA model allows quantification of the errors be-
N
2
Z ( xi ) - Z ( xi + h) tween matching data pairs (Equations 1720). Dispersion
1 ,
g R (h) =
2N
m2
of the data points about the RMA line (SRMA) is estimated
i=1
from
where Z(x) is a value of variable Z at the location x, h is a vector sepa-
rating Z(x) from Z(xi+h) points, and m is the mean of the variable Z(x). S RMA = 2 (1- r )(Var (ai ) + Var (bi )), (17)
When this formula is applied to duplicated pairs of samples whose spa-
tial separation is zero (h = 0), it calculates the value. where r is the correlation coefficient between the values ai
 Quality Control of Assay Data: A Review of Procedures for Measuring and Monitoring Precision and Accuracy M. Abzalov 137

1989; Kane, 1992; CANMET, 1998). The purpose of these

tests is to demonstrate that analytical accuracy is compar-
able to the certified value of a standard and, hence, is ac-
ceptable with 95% confidence.

Statistical Test 1: Estimation Accuracy by Repeat Analy-

ses of Certified Standards, Single Laboratory Case
The most common situation is when one or several cer-
tified standard samples have been included in batches of
samples analyzed at the same laboratory. In such a case,
when several repeat assays of a given standard sample are
available, the analytical accuracy is assessed using statis-
tical tests. A common, and valid, approach is the statistical
t-test. An alternative method is presented in Equation 21
Fig. 2. Scatter diagram and the RMA model (thick line) fitted to paired Fe
grades (wt.%) of blast hole samples. A line with 1:1 ratio (thin) is shown (ISO Guide, 1989; CANMET, 1998):
for reference. The gray triangle shows an area formed by projection of the
data points to the RMA line.
SW2
m - m 2 s L2 + , (21)
and bi, and Var are variances of the values. n
The error on the y-axis intercept (S0) is estimated using where is the certified mean of a given standard sample
Equation 18, and the error on the slope (SSLOPE) is estimated (provided by the maker of the standard); L is the certi-
using Equation 19 for N data pairs: fied inter-laboratory standard deviation of a given standard
sample; m is the arithmetic mean of the replicate analyses
of this certified standard sample in assay batches; SW is the
(1- r ) Mean (ai )
2 estimated intra-laboratory standard deviation of the repli-

S0 = SD (bi ) 2 +
(1 + r ) , (18) cate analysis of the standard sample included in the assay
N
SD ( a )
i
batch; and n is the number of replicate assays of a given
certified standard in the analytical batches. If this condition
is satisfied, then the analytical results are considered ac-
SD (bi ) (1- r 2 ) . ceptable with regard to accuracy.
S SLOPE = (19) The base formula (Equation 21) can be simplified be-
SD (ai ) N cause the usual empirical relationships is that L 2SW
(CANMET, 1998). Consequently, for a large number of
The relative precision error (PRMA (%)) can be estimated replications (n > 10), the above condition can be written
from the RMA model6: as (ISO Guide 33, 1989)
2
S RMA
m - m 2s L. (22)
PRMA (%) = 100 2 , (20)
C If the certified value of the inter-laboratory standard
where C is the mean grade of the paired data (Equation deviation (L) of the reference material is not available,
4). then Equation 22 can be further simplified as (CANMET,
The RMA model is a useful tool for testing duplicated 1998)
data for the presence of bias. For example, the errors on
the slope estimate and/or intercept can be used to test if the m - m 4 SW . (23)
slope of the estimated RMA function is a sampling possi-
bility of one, and if the RMA function intercepts the y-axis Note, however, that the assumption L 2SW might not
at zero. If at least one of these criteria is rejected, then bias be valid in all cases (CANMET, 1998).
is indicated.
Statistical Test 2: Intra-Laboratory Precision, Single
Statistical Tests for Estimation of Performance Laboratory Case
of Certified Standards Comparison of the arithmetic mean of the replicate
analyses of a certified standard against its certified mean
The accuracy of laboratory analyses can be assessed by should be supported by estimation of the standard devia-
statistical tests on certified standard samples (ISO Guide, tion of the replicate analyses of the standard samples. This
is important because poor precision of the standard sample
assays (i.e., if SW is excessively large) can prohibit reliable
6
For consistency with other estimates discussed in this paper, PRMA(%)
detection of analytical biases.
is estimated at 1 standard deviation (i.e., multiplied by 100 in Equation The most common such situation occurs when multiple
20). analyses of a certified standard have been made in the same
138 Exploration and Mining Geology, Vol. 17, Nos. 34, p. 131144, 2008

laboratory. These data are used for calculating the standard
deviation (SW) of replicate analyses of the certified stan-
dard, which should be compared with the corresponding
certified value (C). The analytical precision of a laboratory
is considered acceptable if results satisfy the following sta-
tistical test (ISO Guide 33, 1989):
2 X (2n-1);0.95
( SW sC ) , (24)
n -1
where SW is the standard deviation of replicate analyses
of the standard; C is the certified value of the intra-lab-
oratory standard deviation of the standard; and X (2n-1);0.95 is
the critical value of the 0.95 quartile ( = 0.05) of the (X2)
distribution at (n 1) degrees of freedom, where n is the
number of replicate analysis of the standard.
In practice, at least three repeat analyses of the certi-
fied standard should be available for this test (CANMET,
1998).
Diagnosis of Errors
When poor-quality analytical data have been recognized
from excessive variance of the paired data, or sample bias-
es have been detected, it is necessary to identify the cause
of the error. In this section, two types of diagram are intro-
duced that are particularly useful for preliminary diagnosis
by geological personnel, prior to calling for help from a
specialized sampling consultant.
The first diagram, introduced by Pitard (1998), is known
as the Relative Difference Plot (RDP),
and is used for processing paired
analytical data. The second diagram,
which is widely used in the mining
industry for diagnosing sample biases
and identifying their possible causes
(Leaver et al., 1997; Sketchley, 1998),
is a simple xy plot where assayed val-
ues of the certified standards are plot-
ted on a batch/time basis.
against sequential numbers of the pairs (x-axis); calculated
average grades of the data pairs are shown on the second-
ary y-axis (Fig. 3). A more traditional approach would be
to plot RD(%) values against the average grades of the
data pairs. However, in that case, the diagnostic ability of
this diagram is marred by uneven distribution of the data
between grade intervals. Instead, plotting RD(%) values
against sequential numbers of the data pairs overcomes
this problem. The link between average grades of the data
pairs and their sequential numbers is established by adding
a calibration curve to the RDP diagram (Fig. 3). RD(%)
values usually exhibit a large range of variation; therefore,
interpretation of this diagram can be facilitated by apply-
ing the moving window technique to smooth the initially
calculated RD(%) of the data pairs (Fig. 3).
The example in Figure 3 is based on data collected from
a massive Cu-sulfide project in Russia. Approximately 140
core duplicate samples were analysed in an external reput-
able laboratory as part of the project due diligence. The
results, when plotted on an RDP diagram (Fig. 3), show
that copper assays of low-grade samples (Cu < 1.1%) are
biased. Assayed values have significantly underestimated
the true copper grade of those samples. Another fea-
ture revealed by this diagram is that low-grade samples
(Cu < 1.1%) exhibit excessive precision error that is not
shown by higher grade samples (Cu > 1.1%). These find-
ings triggered a special investigation of the laboratory pro-
cedures, with a particular emphasis on differences between
high-grade and low-grade samples.
The RDP diagram can be used for testing the impact
of data precision against different factors such as sample

Relative Difference Plot (RDP)

The relative difference plot (Pitard,
1998) represents a graphic tool for
diagnosis of the factors controlling
precision error (Fig. 3).
The relative difference is estimated
for each pair of data, expressed as a
percentage:
(ai - bi )
RD(%) = 100 . (25)
(ai + bi ) 2
Calculated RD(%) values are ar-
ranged in increasing order of the aver-
age grades of the data pairs, and then
RD(%) values (y-axis) are plotted
Fig. 3. Relative Difference Plot (RDP) showing Cu(%) grades of duplicated drill core samples
assayed in different labs. The samples are from a Cu-sulfide deposit in Russia. These data are not
included in Table 2 because the duplicate samples have been processed and assayed in an external
laboratory. Open symbols (diamonds) connected by fine tie-lines are RD(%) values calculated from
matching pairs of data (i.e., original sample and duplicate). Average RD(%) value (thick dashed
line) and 2SD values (fine dashed lines) are shown for reference. The solid line is a smoothed line
of the RD(%) values calculated using a moving windows approach. The calibration curve sets the
relationship between RD(%) values on the primary y-axis, the sequential number of the data pairs
plotted along the x-axis, and the average grades of the data pairs plotted on the secondary y-axis.
For example, point A (sequential number of the data pairs is 100) is characterized by an RD(%)
value equal to 16%, and the average grade of the data pair is 1.1% Cu.
 Quality Control of Assay Data: A Review of Procedures for Measuring and Monitoring Precision and Accuracy M. Abzalov 139
size, core recovery, and depth of sample collection. In such
cases, the RD(%) values are arranged according to the fac-
tor under investigation, which is plotted on the secondary
y-axis (instead of the average grades of the data pairs), and
linked by a calibration curve to the sequential number of
the data points shown along the x-axis.
Diagnosis of Accuracy Errors
Diagnosis of sample biases and their possible causes
can be made using a pattern recognition approach (Leaver
et al., 1997; Sketchley, 1998) by plotting assayed values
of certified standards against batch number or time (Fig.
4). This method is based on the fact that specific types of
analytical problems have recognizable patterns on certain
types of diagram. The different distribution patterns of the
analytical results are indicative of the error sources and
types.
This technique is most effective when applied to certi-
fied standards (Leaver et al., 1997; Sketchley, 1998). Good
quality analyses will be characterized by a random distri-
bution of data points around the certified mean value (Fig.
4A), with 95% of the data points lying within two stan-
dard deviations of the mean. The same number of analyses
should fall above and below the mean.
In some cases, the analyzed grades of the standard
samples randomly and significantly differ from the cer-
tified values (Fig. 4B). Presence of such outliers most
likely indicates data transcription errors. This feature does
not imply data bias, but nevertheless indicates poor data
management, and indicates the likely presence of random
errors in the database.
Data bias is easily recognizable by a consistent shift of
standard sample assays from certified values (Fig. 4C).
Usually this occurs because of failed equipment calibra-
tion; it can also be caused by changed analytical proced-
ures in the lab.
A less common distribution pattern is when dispersion
of the standard sample grades suddenly decreases over time
(Fig. 4D). Such a decrease in variability can indicate pos-
sible data tampering (Sketchley, 1998), or at least suggests
that standard samples have been recognized by laboratory
personnel and treated more carefully than other samples. In
such cases, assayed values of the standard samples cannot
be used as reliable confirmation that the assayed samples
lack bias.
Accurate analyses are also characterized by a lack of
systematic data trends on grade versus order of process-
ing diagrams. Trends can be recognized by a systematic
increase or decrease of the assayed values of the standards
over time (Fig. 4E). Another commonly used criterion for
identification of possible trends is when two successive
points lie outside two standard deviations, or when four
successive points lie outside one standard deviation (Leav-
er et al., 1997). Such systematic drifts of assayed standard
values usually indicate instrumental drift. Alternatively,
they can also be caused by degradation of the standard
samples. The author is familiar with cases when the char-
acteristics of standard samples have degraded in compari-
son with their certified values because of inappropriate
storage conditions; for example, storage in large jars that
Fig. 4. Schematic diagrams showing quality control pattern recogni-
tion methods. A. Accurate data, with statistically valid distribution
of the standard values; B. Presence of outliers suggesting tran-
scription errors; C. Biased assays; D. Rapid decrease in data vari-
ability indicating possible data tampering; E. Drift of the assayed
standard values.
140 Exploration and Mining Geology, Vol. 17, Nos. 34, p. 131144, 2008
have not been protected from vibrations from operating
equipment, leading to segregation of heavy minerals to the
bottom of the jar. Hygroscopic samples or standards can
also be affected by storage in unsealed containers. These
problems can be partially overcome if standard materials
are split into small aliquots, preferably using a rotary split-
ter, and stored in sealed containers. Aliquots are then used
as needed for only a small number of analyses.
Discussion and Conclusions
QAQC Practice: Planning and Implementation
This review of recently published QAQC procedures
used in the mining industry (Taylor, 1987; Vallee et al.,
1992; Leaver et al., 1997; Long, 1998; Sketchley, 1998)
and numerous case studies by the author (Abzalov and
Both, 1997; Abzalov, 1999, 2007; Abzalov and Humphreys,
2002; Abzalov and Mazzoni, 2004; Abzalov and Pickers,
2005; Abzalov et al., 2007) shows that reliable control of
sample precision is achieved by using approximately 5% to
10% of field duplicates, and 3% to 5% of pulp duplicates.
Duplicate samples should be prepared and analyzed in the
primary laboratory.
To detect bias in analytical results, it is necessary to in-
clude 3% to 5% of standard reference materials with every
sample batch. A good practice is to use more than one stan-
dard, so that their values span the practical range of grades
in the actual samples. However, standard samples alone
cannot identify biases introduced at different stages of
sample preparation. Anonymity of the standards is another
issue, because standards can be easily recognized in the
sample batches and be treated more thoroughly by labora-
tory personnel. Duplicate samples (i.e., coarse rejects and
pulp) should be analyzed in an external, reputable labora-
tory as part of the accuracy control. It is suggested that at
least 5% of the total analyzed duplicates, including pulp
duplicates and coarse rejects, should be analyzed in the ex-
ternal laboratory.
Duplicate samples should be chosen in such a manner
that all significant stages of the sampling protocol are prop-
erly assessed. However, the main focus of routine duplicate
analyses should be on the very first split (i.e., field dupli-
cates or coarse rejects), because precision error estimated
from these data is a cumulative error, which will include all
subsequent sample preparation and analytical stages. Good
QAQC practice is to collect the bulk of duplicate materials
at the first subsampling stage, whereas subsequent stages,
including pulp duplicates, play auxiliary roles7. Unfortu-
nately, the author has witnessed cases when this simple
rule has been forgotten, and project personnel were col-
lecting unnecessarily large amounts of pulp duplicates,
7
This is the first stage at which the size of the initial sample is reduced
(subsampled) for further treatment. Usually these are duplicates of non-
core drilling samples (e.g., reverse-circulation drilling chips) collected
from splitters at the drill sites, and are therefore conventionally refer-
enced as field or rig duplicates (Long, 1998). Alternatively, for drill
core or grab samples, these can be splits of the coarsely crushed mate-
rial.
whereas field duplicates representing the first subsampling
stage were left unattended.
Duplicate samples should be representative for the
given deposit, covering the entire range of grade values
and mineralization styles; at the same time, their distribu-
tion should maintain, at least partially, the characteristics
of being randomly chosen. To meet these two conditions,
a dual approach is recommended: approximately half of
the duplicates should be collected by a project geologist
with instructions to ensure that they properly represent all
mineralization styles and grade ranges, and that they spa-
tially cover the entire deposit; the other half of the dupli-
cates should be selected randomly. All duplicates should be
placed at random in the assay batch.
Precision Estimates
Various statistical methods for estimating precision have
been assessed by applying them to the same set of dupli-
cate sample analyses (Table 2). Data for this study were
obtained from operating mines and mining projects, in-
cluding published data (Abzalov and Both, 1997; Abzalov,
1999, 2007; Dominy et al., 2000; Roden and Smith, 2001;
Abzalov and Humphreys, 2002; Sinclair and Blackwell,
2002; Abzalov and Mazzoni, 2004; Abzalov and Pickers,
2005; Abzalov et al., 2007) and unpublished reports.
All errors are estimated as relative standard deviations
and expressed as percentages (Table 2). The Thompson-
Howarth method (Equation 3; Thompson and Howarth,
1973, 1976, 1978; Howarth and Thompson, 1976) has been
applied to the average grades of the data sets to make the
estimates by this method (Equation 3) comparable to other
estimates.
Comparison of the results in Table 2 shows that precision
errors produced by the Thompson-Howarth technique are
consistently the lowest among all the reviewed methods.
This result is not surprising because it reflects the assump-
tion in the Thompson-Howarth method that measurement
errors are normally distributed (Thompson and Howarth,
1973, 1976, 1978; Howarth and Thompson, 1976). Based
on this assumption, the method uses the median value of
absolute differences of the data pairs for calculation of
precision error, and this inevitably produces biased results
when errors are not normally distributed.
This study (Table 2) concurs with Stanley and Lawie
(2007b) that conventional Thompson-Howarth error analy-
sis produces significantly biased results when applied to
skewed distributions, and is particularly inappropriate for
estimating analytical precision of samples exhibiting high
nugget effects such as gold and silver ores (Stanley, 2006).
To overcome this problem, Stanley (2006) suggested a
modification to the Thompson-Howarth method that calcu-
lates the root mean squares of the absolute pair differences
instead of their medians. This alternative approach (Stanley,
2006; Stanley and Lawie, 2007b) is a more robust estima-
tor in comparison to the conventional Thompson-Howarth
method because it does not require a normality assumption.
However, this modification is likely to be more sensitive to
outliers, and should therefore be rigorously tested in order
to better understand its possible limitations when applied
 Quality Control of Assay Data: A Review of Procedures for Measuring and Monitoring Precision and Accuracy M. Abzalov 141

Table 2. Comparison of Precision Error Estimated by Different Techniques

Mineralization Metal # Sam-
Type/Deposit (Grade) Grade Range Avg. ples Corr. PTH%*,1 CV(%)2 AMPD3 SR%4 PFP%5 PDFB%6 PRMA%7 Sample Type Data Source
Orogenic gold, Au (g/t) 0.11206 89.600 36 0.92 74.5 105.4 78.7 74.5 75.5 105.2 Repeat channel Dominy et
very coarse and samples al., 2000
nuggety, USA
Archean gold, Au (g/t) 0.0350 4.300 201 0.71 34.4 47.2 66.7 82.9 47.2 46.6 110.1 1st (coarse) split Current study
medium to coarse Au (g/t) 0.01355 1.300 4209 0.98 15.3 24.5 34.6 94.1 24.5 24.5 132.2 Pulp duplicates
grained, Canada
Copper-silver Ag (g/t) 2393 72.310 42 0.98 15.3 21.7 15.0 15.3 15.5 21.1 Channel Sinclair and
veins, Canada samples vs. blast Blackwell, 2002
hole cones
Cu (%) 0.010.97 0.160 42 0.99 13.5 19.2 11.0 13.5 13.5 12.0
Native Cu- Cu (%) 1.171.51 1.370 10 0.55 9.6 13.6 9.8 9.6 10.1 14.5 Pulp duplicates Roden and
mineralization Smith, 2001
Cu-Au porphyry, Cu (%) 0.00014.83 0.100 4707 0.99 5.7 14.1 20.0 21.7 14.1 14.1 30.3 Field duplicates Current study
Australia Au (g/t) 0.00057.01 0.050 4784 0.95 18.6 41.7 59.0 113.9 41.7 41.7 157.7
Cu (%) 0.00025.3 0.400 6346 0.98 1.9 10.5 14.8 17.9 10.5 10.5 25.3 Pulp duplicates
Au (g/t) 0.02276 0.800 14 346 1.00 4.4 17.1 24.2 18.8 17.1 17.0 26.6
Cu-Mo por- Cu (%) 0.00314.4 1.450 398 1.00 1.4 7.1 10.0 2.8 7.1 7.1 3.9 1st (coarse) split Current study
phyry, USA Mo (%) 0.0051.14 0.030 398 1.00 4.0 14.2 20.0 16.0 14.2 14.2 14.2
Cu (%) 0.0159.6 1.430 346 1.00 0.9 2.5 3.6 1.3 2.5 2.5 1.8 Pulp duplicates
Mo (%) 0.0050.315 0.030 346 1.00 2.7 11.5 16.3 5.4 11.5 11.5 7.3
Iron Ore, Deposit Fe (%) 50.6367.37 62.200 228 0.94 0.6 1.4 2.0 1.3 1.4 1.4 1.9 Field duplicates Current study
1, Pilbara, Australia Al O (%) 0.197.38 2.060 228 0.92 5.8 12.4 17.5 19.1 12.4 12.3 26.3
2 3

SiO2 (%) 0.726.0 3.450 228 0.95 7.1 13.7 19.3 21.4 13.7 13.7 30.1
LOI (%) 0.8310.95 4.890 228 0.98 2.2 4.9 6.9 5.1 4.9 4.9 7.2
Iron Ore, Deposit Fe (%) 1.8467.3 51.270 8088 1.00 0.6 2.2 3.0 1.3 2.2 2.1 1.8 Field duplicates Current study
2, Pilbara, Australia Al O (%) 0.1150.66 5.700 8088 1.00 2.3 6.9 9.8 5.6 6.9 6.9 7.7
2 3

SiO2 (%) 0.6895.96 12.560 8088 1.00 2.3 7.0 9.9 4.9 7.0 6.9 6.8
LOI (%) 0.3426.03 7.380 8088 1.00 1.4 2.5 3.5 2.3 2.5 2.5 3.2
Iron oxide Cu-Au Au (g/t) 0.000541.3 0.740 1522 0.93 12.5 25.3 35.7 118.1 25.3 25.2 163.6 1st (coarse) split Current study
mineralization,
Australia
Cu-Au-Fe skarn Cu (%) 0.00312.3 0.910 806 1.00 2.6 8.7 12.4 4.5 8.7 8.5 6.3 Field duplicates Current study
Au (g/t) 0.0535.24 1.390 616 0.99 10.9 20.7 29.2 18.7 20.7 20.6 25.7
Ni-Cu-PGE- Ni (%) 0.00016.82 0.345 587 0.97 12.1 22.1 31.3 43.6 22.1 22.2 59.9 Field duplicates Current study
sulfides, Australia Cu (%) 0.00014.86 0.220 586 0.95 14.6 21.8 30.8 51.7 21.8 21.8 70.3
Co (%) 0.00010.16 0.013 586 0.96 9.4 14.5 20.5 37.2 14.5 14.5 52.2
Pd (g/t) 0.0052.46 0.080 323 0.96 12.3 29.4 41.5 41.1 29.4 29.1 57.8
Ni (%) 0.00015.4 0.170 961 1.00 1.2 11.0 15.6 4.2 11.0 11.0 5.3 Pulp duplicates
Cu (%) 0.0001-15.8 0.180 961 1.00 1.4 4.2 5.9 3.4 4.2 4.2 4.5
Co (%) 0.0001-0.175 0.079 961 1.00 1.7 7.5 10.6 4.4 7.5 7.5 5.9
Pd (g/t) 0.001-1.26 0.109 836 0.97 3.9 17.7 25.1 18.8 17.7 17.8 26.3
Detrital ilmenite Total Heavy 0.7-26.2 7.480 539 0.89 5.4 17.7 25.0 17.5 17.7 17.7 24.7 Field duplicates Current study
sands, Deposit Minerals (%)
1, Africa
Detrital ilmenite
Total Heavy
sands, Deposit 2.4-19.3 8.960 27 0.96 8.1 11.5 10.1 8.1 8.1 13.9 Field duplicates Current study
Minerals (%)
2, Africa
Notes
*
PTH% and SR% errors have been estimated at average (arithmetic mean) grade of the paired data.
1
Equation 3.
2
Equation 6.
3
Equation 7.
4
Equation 13.
5
Equation 10.
6
Equation 12.
7
Equation 20.
CV% = Coefficient of variation (%). This estimator is recommended in the current paper for use as the universal measure of relative precision error in
mine geology applications.
LOI = loss on ignition.
142 Exploration and Mining Geology, Vol. 17, Nos. 34, p. 131144, 2008
to various geological materials.
A second group of estimators include AMPD and other
similar statistical methods (Table 1), which are based on
calculation of the absolute differences between the original
and duplicate samples normalized by the mean grades of
the data pairs (Bumstead, 1984; Shaw, 1997; Roden and
Smith, 2001). Relative errors obtained from this approach
are proportional to coefficients of variation (Stanley, 2006;
Stanley and Lawie, 2007a), and represent nothing more
than the product of the CV and a constant. Hence, the vari-
ous statistics included in this group (e.g., AMPD, HARD)
offer no more information than the CV itself (Table 2).
Stanley and Lawie (2007a) have, therefore, suggested that
the CV be used as a universal measure of the relative pre-
cision error in mine geology applications, instead of the
more confusing AMPD, HARD, and similar measures.
It is important to remember that the average coefficient
of variation (CVAVR(%)) is calculated as a square root of
the average relative variance (Equation 6). The same ap-
proach, which is consistent with the additivity principle,
must be used if precision error is estimated using AMPD
and other measures proportional to the coefficient of varia-
tion (Table 1)8. In other words, the correct procedure for
obtaining an average AMPD value should also be based on
calculating average relative variance and then taking the
square root of it. However, this principle was not followed
by Bumstead (1984) and Roden and Smith (2001), who
used an average precision error calculated as the arithmetic
mean of the AMPD values of the duplicated samples. This
is another reason to avoid measurements like AMPD and
HARD, whose statistical meaning is less evident than the
CV, and which cause confusion and incorrect treatment of
the data.
An alternative geostatistical approach is based on meas-
uring data precision by applying formulae of the vario-
grams to duplicated samples (ai and bi; e.g., Garrett, 1969).
The two most common methods used for QAQC purpose
are the pair-wise relative variogram (Equation 9) and the
relative variogram (Equation 13). However, it is easy to
see that when a pair-wise relative variogram is applied to
duplicated samples, it simply measures the relative vari-
ance of the paired data. The square root of this value is
equal to average coefficient of variation:
2 N (a - b )2
i
PFP (%) = 100
N
(a + b ) = CV
i
2 AVR (%) . (26)
i =1 i i
Hence, the two approaches, one that uses the coefficient
of variation (CVAVR(%); Equation 6) as a universal measure
of the relative precision error (Stanley and Lawie, 2007a),
8
Standard deviation is not an additive parameter, and therefore its aver-
age value cannot be calculated as the arithmetic mean of the standard
deviations of the individual data pairs. Conversely, variance is an addi-
tive parameter, and therefore the mean variance can be calculated. The
average standard deviation is then derived by taking the square root of
the mean relative variance (Equation 6).
and the second that uses a geostatistical approach based on
the application of a pair-wise relative variogram (PFP(%);
Equation 10) for measuring precision error, are identical
because both are based on calculating the average relative
variance of the paired data. Not surprisingly, both estimates
produce the same results (Table 2).
Other geostatistical tools, such as the lognormal vario-
gram (Garrett, 1969) or the relative variogram (Equation
13; Eremeev et al., 1982), are not suitable for estimation
of average precision error because of their sensitivity to
outliers. In particular, when a relative variogram (Equation
13) is applied to strongly skewed data without subdivid-
ing them onto grade classes, the results significantly differ
from their calculated CVAVR(%) values (Table 2).
The approach suggested by Francois-Bongarcon (1998;
Equations 1112) calculates the ratio of the difference be-
(a - b )
tween the paired data to their sum ( (a + b ) ) and then estimates
i
i
i
variance of this complex variable. Results of this method
are similar to the average coefficient of variation (Table
2). However, Equation 11 seems to be unnecessarily com-
plicated in comparison to the conventional CVAVR(%) ap-
proach (Equation 26).
The RMA model (Fig. 2) is another QAQC technique
that is becoming increasingly popular among geoscientists
(Sinclair and Bentzen, 1998; Davis, 2002; Sinclair and
Blackwell, 2002). This method consists of the calculation
of the RMA line (Equations 1416) and related parameters
(Equations 1720), and is particularly useful for identify-
ing bias between paired data (Fig. 2). This method can be
used to calculate the precision error estimate from disper-
sion of the data points about the RMA function (Equation
20). However, it is shown here that the errors estimated
from this model (PRMA(%)) can significantly differ from
CVAVR(%) values (Table 2). These differences are likely due
to sensitivities of the RMA model to the presence of out-
liers, which makes this technique inappropriate for strongly
skewed distributions.
In summary, the author concurs with the proposal of
Stanley and Lawie (2007a) that CVAVR(%) be used as the
universal measure of relative precision error. Based on
numerous case studies, the appropriate levels of sample
precisions are proposed for different types of deposits in
Table 3, and it is suggested that these levels be used as ap-
proximate guidelines for assessing analytical quality. It is
important to remember that the values in Table 3, although
based on case studies of the mining projects, might not be
appropriate always because mineral deposits can signifi-
cantly differ by the grade ranges, statistical distribution of
the studied values, mineralogy, textures, and grain sizes.
Accuracy Tests
The accuracy of analytical data is quantified by statis-
tical comparison of the arithmetic mean of the replicate an-
alyses of a certified standard with its certified mean com-
position (Equations 2123). The purpose of these tests is to
demonstrate that analytical accuracy is comparable to the
certified value of a standard, and is acceptable with 95%
confidence. These tests should be supported by estimation
of the standard deviation of the replicate analyses (Equa-
 Quality Control of Assay Data: A Review of Procedures for Measuring and Monitoring Precision and Accuracy M. Abzalov 143

Table 3. Best and Acceptable Levels of Precision Errors (CVAVR(%)) suggests the use of RMA diagrams as
Mineralization Best Acceptable a routine supplement to statistical cal-
Type / Deposit Metal Practice Practice Sample Type culation of the precision error. When
Gold, very coarse grained Au (g/t) 20 (?) 40 Field duplicates the estimated CVAVR(%) exceeds the
and nuggety allowed tolerance level (Table 3), an
Gold, coarse to medium Au (g/t) 20 30 Field duplicates RDP diagram can be used for a more
grained Au (g/t) 10 20 Pulp duplicates
detailed analysis and diagnosis of er-
rors.
Cu-Mo-Au porphyry Cu (%) 5 10 Field duplicates
Mo (%) 10 15 Acknowledgments
Au (g/t) 10 15
Cu (%) 3 10 Pulp duplicates The author expresses his sincere
Mo (%) 5 10 gratitude to all his colleagues in the
Au (g/t) 5 10 mining industry, in particular from
WMC Resources, Rio Tinto, BHPB,
Iron ore Fe (%) 1 3 Field duplicates
and Norilsk Nickel, for many stimulat-
Al2O3 (%) 10 15 ing discussions and useful comments
SIO2 (%) 5 10 on an earlier version of this paper.
Loss on Ignition (%) 3 5 C. Stanley is thanked for assistance in
Cu-Au-Fe skarn and Iron Cu (%) 7.5 15 Field duplicates obtaining the most recent papers on
oxide associated Cu-Au Au (g/t) 15 25 sampling and measurements errors.
Review and useful comments by M.
Cu (%) 5 10 Pulp duplicates
Rayner, A. Sinclair, an anonymous
Au (g/t) 7.5 15
journal reviewer, and, in particular,
Ni-Cu-PGE-sulfides Ni (%) 10 15 Field duplicates very helpful editorial comments by J.
Cu (%) 10 15 Richards are gratefully acknowledged.
PGE 15 30
Ni (%) 5 10 Pulp duplicates References
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