Estimating sampling errors for major and trace elements in geological

materials using a propagation of variance approach

Clifford R. Stanley
Department of Geology, Acadia University, Wolfville, Nova Scotia, B49 2R6 Canada (e-mail: cliff.stanley@acadiau.ca)

ABSTRACT: Sampling errors produced when geological materials (rocks, soils, tills,
drainage sediments) are collected have been estimated empirically using variance
decomposition methods or theoretically using Poisson or binomial statistics.
Unfortunately, historical distribution-based approaches assume that the element of
interest occurs in only one mineral. Although this may be true in some cases, most
major oxide and many trace elements reside in more than one mineral in most
geological materials. As a result, historical distribution-based approaches do not
estimate sampling errors correctly.
An alternative theoretical approach to sampling error estimation is proposed that
employs both Poisson and hypergeometric statistics, depending on whether the
elements of interest reside in rare or common grains. It is intended for use in advance
of sampling to ensure that samples in a survey will be colleted in sufficient size to
achieve a desired level of sampling precision. This method requires estimates of the
proportions, sizes and compositions of the minerals making up the geological
material, and thus is based on information readily available from a few (orientation)
samples of the material to be sampled.
This approach accommodates cases where more than one mineral contains an
element of interest. It involves first estimating the sampling error for the minerals
present in the geological material. Then, the mineral sampling errors are used to
make estimates of the sampling error of all elements within these minerals
simultaneously using a simple propagation of variance approach. An EXCEL
spreadsheet is provided that undertakes the relevant calculations, and this can be
adapted to consider any suite of minerals and elements in geological materials.

KEYWORDS: Sampling error, sample preparation, binomial distribution, hypergeometric distribution,

Poisson distribution, variance propagation

INTRODUCTION The fundamental controls that determine the magnitude of

Geochemical variations attributable to sampling and prepar-
ation (or sub-sampling) errors have been considered by a variety
of authors (Wickman 1962; Wilson 1964; Kleeman 1967; Vis-
man 1969; Engels & Ingamells, 1970; Ingamells & Switzer 1973;
Ingamells 1974a, b, 1981; Gy 1974, 1979; Cheng 1995; Clifton
et al. 1969; Stanley 1998). These authors generally conclude that
in many cases, sampling errors may represent the majority of
error inherent in a geochemical analysis, and these errors may be
so large as to obscure the underlying controls on the geochemi-
cal composition. Field-based studies comparing the magnitude
of sampling and analytical error (e.g. Baird et al. 1967; Morton
et al. 1969; Cameron et al. 1979) confirm these conclusions.
More recently, the new analytical methods that have signifi-
cantly reduced analytical error (Hall 1993) have made sampling
error an even larger proportion of the total measurement error.
Because geochemical analysis typically involves collecting a
(hopefully) representative sample and reducing the size of that
sample to a mass convenient for instrumental analysis, knowl-
edge of the actual magnitude of sampling and preparation error
is critical to developing sampling and preparation strategies that
do not introduce significant error.
Geochemistry: Exploration, Environment, Analysis, Vol. 3 2003, pp. 169–178
sampling error are: (1) sample size; (2) grain size(s) of the
mineral(s) hosting the element of interest; (3) the abundance(s) of
the mineral(s) containing the element of interest; and (4) the
concentration(s) of the element of interest in the host mineral(s).
The last three of these factors are characteristics of the
geological material sampled, and typically determine the size of
the sample necessary to obtain a desired level of sampling or
preparation precision. Essentially, the ‘law of large numbers’
dictates that the larger the sample, the smaller the sampling
error. However, collecting too large a sample will introduce
additional sample preparation costs, so determining how large a
sample to collect to achieve, and not over-achieve, a specified
level of sampling error is a critical objective in geochemical
survey design.
Two fundamental approaches have considered these four
factors to produce methods in which to quantify the magnitude
of sampling or sample preparation error: empirical approaches
(Visman 1969; Gy 1974, 1979) and theoretical approaches
(Wickman 1962; Wilson 1964; Kleeman 1967; Clifton et al.
1969; Engels & Ingamells 1970; Ingamells & Switzer 1973;
Ingamells 1974a, b, 1981; Cheng 1995; Stanley 1998).
1467-7873/03/$15.00  2003 AEG/Geological Society of London
170 C. R. Stanley
The most popular empirical approach involves Pierre Gy’s
sampling theory (Gy 1974, 1979). This employs a number of
empirical constants to describe the physical, mineralogical and
geochemical characteristics of the samples under consideration.
This approach can be applied to both rare and common mineral
grain sampling scenarios, and has been proven to be a useful
method of determining sampling and preparation error in many
geochemical samples (Gy 1974, 1979; Ottley 1983; Sketchley
1997; Francois-Bongarcon 1998). However, Gy’s method does
require the estimation of a variety of empirical factors generally
determined from prior sampling results (Sketchley 1997;
Francois-Bongarcon 1998). As a result, Gy’s sampling tech-
nique (1974, 1979) cannot readily be used to estimate appro-
priate sample size in advance of sampling.
In contrast, theoretical approaches utilize statistical distri-
butions to quantify the magnitude of sampling and preparation
error a priori. As such, they require a simple sampling scenario
so that the underlying statistical assumptions can be met. In
order to achieve this simple scenario, the ‘equant grain model’
(Stanley 1998), or equivalent assumptions, have typically been
invoked (Clifton et al. 1969; Visman 1969; Ingamells & Switzer
1973; Cheng 1975; Ingamells 1974a, 1974b, 1981). The ‘equant
grain model’ assumes that: (1) all of the mineral grains have the
same size; (2) the element of interest resides in only one
mineral; (3) the concentration of the element of interest in that
mineral is constant; and (4) the compositions of all other
(gangue) mineral grains are the same.
If the mineral containing the element of interest is a rare
grain (nugget), then the Poisson distribution can be used
effectively to quantify the sampling error (Wickman 1962;
Ingamells & Switzer 1973; Ingamells 1974a, b, 1981; Clifton
et al. 1969; Stanley 1998). In contrast, if the mineral grain
containing the element of interest is common (making up
a significant proportion of the mineral grains), then the
binomial distribution has been invoked in an attempt to
quantify the sampling error (Wilson 1964; Kleeman 1967;
Engels & Ingamells 1970; Ingamells & Switzer 1973; Cheng
1995).
Unfortunately, use of the binomial distribution in this
instance is not statistically valid. This is because the binomial
theorem applies to trials where there is random sampling with
replacement (Spiegel 1975). The replacement ensures that the
probabilities do not change from trial to trial. Unfortunately,
geological materials are aggregates of a large number of mineral
grains. As a result, sampling a geological material can be
considered as a series of many random selections of mineral
grains. However, once a grain is selected as part of the sample,
it is not replaced. Thus, the probabilities of collecting mineral
grains of interest change during this conceptual series of
random selections, and the appropriate distribution to model
the scenario is the hypergeometric distribution. This is because
the hypergeometric distribution applies to cases of random
sampling without replacement (Spiegel 1975).
Furthermore, virtually all theoretical approaches estimating
sampling or preparation error involving Poisson or binomial
statistics assume that the element of interest is contained within
only one mineral. Theoretical approaches using binomial statis-
tics have been developed to consider cases where the element
of interest is contained in trace amounts in the gangue mineral
(Engels & Ingamells 1970; Cheng 1995), but the mathematics
have generally proven to be unwieldy. Whereas the element of
interest may reside in one mineral in some cases (e.g. Au in
native gold, Zr in zircon), this is not true in general. As a result,
the sampling error estimation approaches developed to date
cannot rigorously make accurate estimates of sampling errors
for most elements in geological materials.
The following theoretical approach to sampling error esti-
mation overcomes these two problems. It can be employed
using either or both Poisson and hypergeometric statistics to
simultaneously address sampling errors associated with rare and
common grains. Furthermore, it does not assume that only one
mineral contains the element of interest. Finally, because
different elements reside in different minerals that have different
grain sizes and proportions, different sample sizes may be
necessary to achieve a specific level sampling error for different
elements. The theoretical approach developed below allows
calculation of the magnitude of sampling error for all elements
simultaneously, and thus also avoids this further complication.
Input required to estimate sampling error includes only the
proportions, sizes and compositions of the minerals making up
the geological material. As a result, this technique can be
employed in advance of a geochemical survey using information
derived from a small number of (orientation) samples.
APPROACH
In order to develop a sampling error estimation method with
the above characteristics, the relationship between the compo-
sition of a geological material and its mineral proportions must
be formalized. Consider a geological material that contains a
suite of several (p) minerals. The concentration of an element in
the geological material can be determined from the relative
proportions and compositions of the contained minerals,
according to the equation:
p
Xi = &N X
j=1
j ij (1)
where X is a mass concentration, N is a mineral proportion (in
mass terms), j is a mineral index and i is an element index. An
equation of this form exists for every (major, minor and trace)
element in a geological material, and these equations establish
the relationship between a geological material’s geochemical
and modal composition.
For example, consider a granite rock composed of quartz,
albite, potassium feldspar and phlogopite. The composition of
SiO2 in this granite is thus governed by:
XSiO2 = NQTZXSiO2,QTZ + NALB XSiO2,ALB + NKSP XSiO2,KSP +
NPHLXSiO2,PHL
Similar equations govern the concentrations of other major,
minor and trace elements in the rock. For example:
XK2O = NQTZXK2O,QTZ + NALB XK2O,ALB + NKSP XK2O,KSP +
NPHLXK2O,PHL
Thus, with knowledge of the geological material’s mineral
proportions and compositions, the bulk composition of a
geological material can be deduced from the set of relations
represented by Equation 1.
Variance propagation
If the element concentration measurement errors associated
with sampling a geological material are desired, then simple
error variance propagation can be used to estimate these errors,
provided the errors in the mineral proportions and element
concentrations are known. The equation to estimate these
sampling errors can be obtained from a generative formula
 Sample errors for elements in geological materials 171

derived from a Taylor series first order expansion (Meyer 1975;

Rees 1984; Stanley 1990; Vacher 2001):

p 2 p
1 p

f2~X! = &~
j=1
Xj Xj !
f
2 + 2
& &~Xf !~Xf !

k = 1j = 2
j k
XjXk (2)

Because the mineral proportions and mineral compositions

are independent, the second summation term in Equation 2
cancels (because all
XjXk=0), and the sampling error propa-
gation equation associated with Equation 1 reduces to:

X2 i = &~

j=1
2 2
NjX ij + N2j
X2 ij! (3)

where the
2 are the variances of the associated mineral

proportions and mineral compositions.
To solve Equation 3 and determine the sampling errors for
any element in a geological material requires knowledge of both
the mineral proportions and mineral compositions in that Fig. 1. Schematic geological material containing six different minerals
material, as well as the measurement errors associated with each of differing size, shape, colour and volume proportion.
mineral proportion and mineral composition. Unfortunately,
Equation 3 becomes complicated if significant compositional wish to consider cases where more than one mineral contains
variability exists in some minerals. As a result, let us assume, for the element of interest and where minerals have different sizes
the moment, that every mineral in the geological material has an and shapes, we need to consider several equant grain models,
invariant composition, and that we either know this compo- one for each mineral of different size and shape (Fig. 1). As a
sition, can assume it as ideal, or can estimate it based on result, we create several equant grain models, each involving
petrological principles. Note that below we will consider a equant grains with a size and shape equal to the size and shape
strategy that will accommodate variations in composition, so of the target mineral, as determined from prior hand sample or
that the more general case involving mineral composition thin section examination.
variations can be considered. Thus, for a large mineral, the geological material is concep-
If the compositions of all minerals are invariant, we can tually broken up into equant grains the size of the large mineral.
substantially simplify Equation 3: Consequently, the large mineral will conceptually occur fully
liberated in the equant grains, but the smaller minerals will be
p
composited into the larger equant grains (Fig. 2). For a small

X2 i = &~

j=1
2 2
NjX ij ! (4) mineral, the geological material is conceptually broken up in a
different way such that the equant grains have a size equal to the
small mineral. Consequently, the small mineral will occur
because all
X2 ij=0. conceptually fully liberated in individual grains, but the larger
As a result, the error in the mineral proportion estimates and minerals will be broken up into the smaller equant grains (Fig.
the concentrations of the elements in each mineral are all that 3). Finally, for a medium-sized mineral, the geological material
are required to estimate the sampling error in each element is conceptually broken up such that the equant grains have a
concentration in the geological material. Using measured, size equal to the medium-sized mineral. In this case, the smaller
assumed or constrained mineral compositions to determine the minerals will be conceptually composited into the medium-
element concentrations in each mineral, the element sampling sized equant grains, whereas the larger minerals will be concep-
errors become functions of only the errors on the modal tually broken up into the medium-sized equant grains (Fig. 4).
estimates of the minerals: Once these equant grain models are invoked, the mineral
proportion sampling errors for minerals that are common in

X2 SiO =
N2
~100.00%!2 +
N
2
~68.74%!2 +
N
2
~64.76%!2 + the sample can be estimated for each mineral using the
2
2
QTZ ALB KSP
hypergeometric distribution, whose variance is:

N PHL
~41.00%!2
and:
2 = np~1
p! N
n
~ ! (5)
N
1

X2 K O =
N
2
~0.00%!2 +
N
2
~0.00%!2 +
N
2
~16.92%!2 +
2 QTZ ALB KSP In this application,
2 is the variance of the hypergeometric
2

N PHL
~10.71%!2 distribution and has units of number of grains squared, n is the
effective number of equant grains in the sample (and must
Thus, determining the mineral proportion sampling errors is generally be greater than 20 for the hypergeometric variance
all that is required to determine the magnitude of sampling error formula to apply), p is the proportion of the mineral grain of
on the bulk composition for the geological material. interest in the sample, and N is the effective number of equant
grains in the population. The effective number of equant grains
Common mineral proportion sampling errors in a sample can be determined for each mineral from the
In order to estimate the sampling error for a geological material, given sample size and the grain size of the mineral of interest
the equant grain model must be invoked. However, because we using:
172 C. R. Stanley
Fig. 2. Schematic geological material conceptually broken up into
equant grains the size of the large dark gray square mineral of Figure
1 (now darkened for illustrative purposes). Note that in order to
invoke the ‘equant grain model’, the other equant grains of the same
size are composites of several other minerals. The large dark gray
square mineral comprises 17.36 % (25 of 144 equant grains) of the
geological material.
Fig. 3. Schematic geological material conceptually broken up into
equant grains the size of the small dark gray square mineral of Figure
1 (now darkened for illustrative purposes). Note that the larger grains
have been broken up into equant grain size to be able to invoke the
‘equant grain model’. The small dark gray square mineral comprises
14.93 % (86 of 576 equant grains) of the geological material.
n=M (6)
m
(Clifton et al. 1969; Stanley 1998) where M is the mass of the
sample and m is the mass of a grain of the mineral of interest.
The proportion of the mineral grain of interest can be estimated
from prior hand sample or thin section examination. As a result,
the additional only parameter necessary to estimate is N, the
effective number of grains in the population.
The effective number of grains in the population is ideally a
function of the geometry and sampling density of the geochemi-
Fig. 4. Schematic geological material conceptually broken up into
equant grains the size of the elongate white mineral of Figure 1 (now
darkened for illustrative purposes). Note that, in order to be able to
invoke the ‘equant grain model’, the smaller minerals have been
composited into equant grains, whereas the larger minerals have been
broken up into equant grains. The elongate white mineral comprises
15.10% (29 of 192 equant grains) of the geological material.
cal survey undertaken. For example, if the geochemical survey
is a one-dimensional traverse across continuous bedrock expo-
sure where samples are collected at random within 25 m
intervals, and if the sample is a 10 cm  10 cm  10 cm rock
(c. 2.7 kg in size), the population from which each sample is
collected can be considered to be a strip 10 cm wide, 10 cm
deep and 25 m long. Although this definition of the population
might at first appear arbitrary, if the survey is truly a traverse,
then samples should be collected along a line. As a result, this
definition of the population is entirely consistent with the
survey design. Given the above sample and population,
the volume of the actual sample is 1/250th of the volume of the
population. Consequently, N/n = 250, and this value can be
thought of as the inverse of the one-dimensional sampling
density (d = 1/250; a unitless quantity).
Alternatively, if the sample is 30 cm  30 cm  30 cm in
size (c. 72.9 kg in size), then the population can be considered
as a similar strip 30 cm wide, 30 cm deep, and 25 m long. As a
result, N/n is lower (= 83.33; d = 1/83.33) because the sample
size is larger. Alternative scenarios where samples are not
universally available can also be considered. For example, if the
outcrop exposure for the above survey was only 25%, the
population size would drop accordingly, and N/n for 30 cm3
samples would drop to 20.83. Finally, if the geochemical survey
involves collection of 1 m long sections of continuous half
diamond (NQ) drillcore, then the sample mass will be c. 2.5 kg.
However, because only two samples can be collected from each
meter of drill core (one half of the core, or the other half), the
one-dimensional sample density is large (d = 1/2; N/n = 2).
In a similar manner, if the geochemical survey is a two-
dimensional 50 m square soil grid, and the samples are 10 cm 
10 cm  10 cm in size (c. 2 kg in mass), then the population
from which a sample can be collected is a square right prism
50 m by 50 m wide by 10 cm thick. In this case, N/n will equal
250,000 and the two-dimensional sampling density will be
1/250,000 (and is again unitless).
In geochemistry, the size of the population from which a
sample is collected has not historically been conceived in the
 Sample errors for elements in geological materials
Fig. 5. Schematic diagram to illustrate geochemical sample formats.
Each small square represents a mineral grain, and the two large grids
represent two grain populations.
above manner. Nevertheless, the sample density and sample
size exert direct control on the N/n ratio, and this ratio can be
used to quantify the size of the underlying population for each
sample (N) by simple multiplication of the ratio by n (from
Equation 6).
If population size is to be conceived in this way, then in order
to use the hypergeometric distribution in the sampling error
variance calculation (Equation 5), the grains that make up the
sample should be collected individually and at random grain by
grain (Fig. 5, top). The 36 scattered 1  1 small shaded squares
in Figure 5 graphically represent these individual grains. Obvi-
ously, while ideal, this is not logistically possible for virtually all
geochemical surveys, where single grab samples or composites
consisting of a small number of sub-samples are typically
collected. As a result, most geochemical samples are derived
from one or a few locations (as composites) from within the
population area (Fig. 5, bottom). The large 6  6 shaded square
in Figure 5 illustrates how the grains are typically derived from
one spot. Thus, technically, sampling errors cannot be estimated
for most geochemical surveys.
However, if the population area is compositionally homoge-
neous, then the collection of a sample composed of individual
grains from a variety of random locations, and the collection of
a sample where all the grains are derived from a randomly
chosen single point or small set of points, are equivalent from
a probability point of view (Dr. Paul Cabilio, Acadia University,
pers. comm. 2002). As a result, the use of the hypergeometric
173
variance to estimate sampling error is possible if population
homogeneity can be assumed and the sample design involves a
random-stratified geometry. If the population is not homoge-
neous, then random composite sampling is required to ensure
that the resulting sample is representative of the entire popu-
lation. Only then will the resulting sample exhibit equivalent
sampling error to an idealized sample collected grain by grain.
The extent of composite sampling necessary is dependent on
the level of heterogeneity within the population, and a larger
number of smaller sub-samples would necessarily have to be
collected from extremely heterogeneous populations.
Once N/n has been determined, and n has been calculated
from the grain size and sample size (Equation 6), N can be
determined through simple multiplication of N/n by n. Thus,
provided that: (1) volume-based mineral proportion estimates
derived from hand sample or thin section inspection are
converted into mass-based mineral proportion values; (2) mass-
based mineral compositions are known, assumed or con-
strained; and (3) the sample size and mineral sizes are known, all
necessary parameters required for determination of the hyper-
geometric mineral sampling variances are available and the
overall element sampling variance can be calculated using
Equation 4.
One should note that if N/n is very large, then Equation 5,
converges to:

2 = np~1
p! (7)
because (N
n)/(N
1) => 1. This equation describes the
variance of a binomial distribution. As a result, the convergence
of the hypergeometric variance on the binomial variance as N/n
=> ` illustrates that the use of binomial statistics by previous
authors (Wilson 1964; Kleeman 1967; Engels & Ingamells 1970;
Ingamells & Switzer 1973; Cheng 1995) to estimate sampling
error was not a bad assumption for reconnaissance-type sur-
veys, and was a substantial improvement over previous practice.
However, because the possible population sizes (N) for com-
monly used geochemical surveys (e.g. drill core, soil grids) can
vary significantly relative to n, the binomial variance approach is
not generally valid. Nevertheless, it can be shown that, provided
N is several orders of magnitude larger than n, the estimated
variances from Equations 5 and 7 are virtually identical. As a
result, in most two-dimensional geochemical surveys (e.g. soil
grid and drainage sediment surveys; particularly reconnaissance
surveys) which commonly have large N/n ratios (say > 10 000),
the binomial variance formula can be used without significant
bias. However, for most one dimensional traverses (e.g. drill
core sampling programs or soil/bedrock traverses), the hyper-
geometric variance formula must be used.
For example, if we can assume that the synthetic rock sample
presented in Figure 1 was collected as part of a two-dimensional
rock survey with sample density and sample size such that N/n
= 10,000, then the mineral sampling variances can be calculated
using either hypergeometric or binomial variance formulae
(Equations 5 or 7). Table 1 presents the concentrations and
calculated binomial and hypergeometric errors (they are equal)
for each mineral in the synthetic rock under this assumption.
However, if the synthetic rock sample of Figure 1 was collected
as part of a one-dimensional survey with N/n = 100, then
the mineral sampling variances can be calculated accurately
using only the hypergeometric variance formula (Equation 5).
Table 2 presents the corresponding results under this assump-
tion. Significant differences exist in the estimated sampling
errors for these two surveys, and these differences are solely a
function of the geometry and sample density of the geochemical
survey.
174 C. R. Stanley

Table 1. Calculated one standard deviation coefficients of variation for the six minerals in the synthetic rock of Figure 1, assuming N/n = 10 000 (consistent with a reconnaissance
lithogeochemical survey).

Figure Size Shape Color N n x p (%)
x
p CV%

2 large square dark gray 1,440,000 144 25 17.4 4.6 3.2 18.4
3 small square dark gray 5,760,000 576 86 14.9 8.6 1.5 10.0
small square light gray 5,760,000 576 41 7.1 6.2 1.1 15.1
small square white 5,760,000 576 205 35.6 11.5 2.0 5.6
4 medium elongate white 1,920,000 192 29 15.1 5.0 2.6 17.2
medium elongate light gray 1,920,000 192 19 9.9 4.1 2.2 21.8

N – number of equant grains in the population for each model; n – number of equant grains in the sample; x – number of grains of the mineral of interest in
the sample p – proportion of the mineral of interest in the sample, p = x/n;
x – one standard deviation sampling error on the number of grains of the mineral
of interest in the sample based on hypergeometric statistics;
p – one standard deviation sampling error on the proportion of grains of the mineral of interest in
the sample based on hypergeometric statistics; CV% – coefficient of variation for the number and proportion of grains of the mineral of interest in the sample
(they are equal).

Table 2. Calculated one standard deviation coefficients of variation for the six minerals in the synthetic rock of Figure 1, assuming N/n = 10 (consistent with a detailed lithogeochemical
survey). See Table 1 caption for explanation of table headings.

Figure Size Shape Color N n x p (%)
x
p CV%

2 large square dark gray 1,440 144 25 17.4 4.3 3.0 17.2
3 small square dark gray 5,760 576 86 14.9 8.1 1.4 9.4
small square light gray 5,760 576 41 7.1 5.9 1.0 14.3
small square white 5,760 576 205 35.6 10.9 1.9 5.3
4 medium elongate white 1,920 192 29 15.1 4.7 2.5 16.3
medium elongate light gray 1,920 192 19 9.9 3.9 2.0 20.3

A ‘rule of thumb’ that provides insight into which distri- and:

bution variance formula to use to estimate sampling error is that
reconnaissance surveys generally have large N/n, and thus can
have their sampling variances estimated using the either the
hypergeometric or binomial variance formula. However, de-
tailed and follow-up surveys typically have low N/n, and thus
require use of the hypergeometric variance formula.
Note that because (N
n)/(N
1) is always c 1, the
hypergeometric sampling errors will always be smaller than the
binomial sampling errors. This bias produces some rather
undesirable effects when one attempts to reduce sampling error.
Reducing sampling error requires that the size of the sample be
increased. This is because the relative sampling error (measured
using the coefficient of variation, in percent; CV%) is a function
of n, the effective number of equant grains in the sample. For
the hypergeometric distribution:
~1
p!
n=   ~100%!2 (11)
p~CV%!2
for hypergeometric and binomial distributions, respectively.
Consequently, if the sampling error is over-estimated because
the binomial variance formula was used, then calculations to
determine the appropriate sample size to achieve a specific level
of sampling precision will over-estimate the sample size re-
quired. Although many would consider this desirable because it
would produce a ‘conservative’ result, this philosophy is actually
misguided. Collecting a larger than necessary sample may
require additional costs in terms of time and manpower, leading
to a less cost efficient and less effective geochemical survey.
Furthermore, over-estimation of sampling error could nega-
tively impact subsequent data analysis. Statistical tests on the

CV % = 100%  Π~1
p!~N
n!
np~N
1!
(8)
geochemical results may indicate that some of the real but
subtle geochemical variations observed are not statistically
significant solely because they do not exceed the over-estimated
measurement errors. As a result, critical geological information
and for the binomial distribution:
may be lost by over-estimating sampling error simply because
the statistical critical value was ‘conservatively’ set too high. For
CV % = 100%  Π~1
p!
np
(9) example, if the sampling error for Si is conservatively estimated
at 1 wt. % (when it is in fact 0.25 wt. %), subtle variations with
magnitudes less than 1 wt. % but greater than 0.25 wt. % would
In both of these equations, CV % is equal to the sampling not be considered significant, even though they would be
error standard deviation divided by the mean (observed) significant with a correctly estimated sampling error. Thus, this
number of target mineral grains (x = np), expressed in percent. potential loss of information would also result in a less efficient
Thus, increasing the size of the sample (n), decreases the relative and effective geochemical survey. As a result, over-estimating
sampling error. By rearranging Equations 8 and 9, one can sampling error can produce results that are as bad as under-
determine the size of the sample necessary to obtain a desired estimating sampling error (which could result in the collection
level of relative sampling error using: of unrepresentative samples and/or data analysis conclusions
that are not supported by the data). Thus, the use of the
~1
p!N
n=   ~100%!2 (10) hypergeometric distribution variance formula is recommended
p~CV %! ~N
1! + ~1
p!
2
to produce accurate sampling error estimates.
 Sample errors for elements in geological materials
Rare mineral proportion sampling errors
The above discussion has focused on sampling errors associated
with mineral grains that are common in samples of a geological
material. If the mineral of interest is not a common grain, then
a similar approach may be undertaken using a different statistical
distribution to estimate the level of sampling error.
Rare minerals, also known as nuggets, are typically governed
by Poisson statistics (Clifton et al. 1969; Stanley 1998). Fortu-
nately, the formula describing the sampling variance for the
Poisson distribution is much simpler than the formula for the
hypergeometric distribution:

2 = x (12)
where x is the number of nuggets in the sample (x = np).
Obviously, if one knows the proportion (p) and size of the rare
mineral grain, and the effective number of equant grains in the
sample, one can determine how many of the rare mineral grains
reside in the sample by simple multiplication. If x is small (<
20), the mineral is a candidate for modeling its sampling
variance using the Poisson distribution, and the mineral
sampling variance can be determined using Equation 12. The
relative error associated with sampling a rare grain can be
determined using Equation 13, and the size of a sample
necessary to achieve a specific relative sampling error can be
determined using Equation 14:
CV % = 100% (13)
=x
~100%!2
n= (14)
p~CV %!2
Once the sampling variance for the rare grain has been
determined, Equation 4 can then be used to assess the
geochemical sampling error. In this way, using hypergeometric
and Poisson variance approaches, both common and rare
mineral grains containing an element of interest can be simul-
taneously addressed by this propagation of variances approach.
Variations in mineral sizes and compositions
The above discussion has assumed that the compositions of the
minerals do not vary. As a result, the second term in the
summation of Equation 3 equals zero, and the calculation of
the sampling error employs the simplified Equation 4. This
assumption of constant composition can be avoided by con-
sidering the observed range in mineral composition as a suite of
minerals with different compositions. For example, if the
plagioclase composition in a sample was observed to be
bimodal, with 30% having a composition of AN50–60 and 70%
having a composition of AN10–20, then plagioclase could be
considered as two different minerals, one with a composition of
AN55 and one with a composition of AN15. The proportions of
each plagioclase composition would be adjusted to reflect the
30:70 proportion of plagioclase with AN50–60 and AN10–20
compositions. In this way, mineral composition variations can
be addressed, and the level of detail used to describe the mineral
compositional variations can be made commensurate with the
precision required for the sampling error estimate and the
ultimate geochemical survey objectives.
Similarly, if there is a range in grain sizes for a mineral, the
mineral could be considered as a suite of minerals with different
equant grain sizes. For example, potassium feldspar could exist
as both a phenocryst and a groundmass mineral in a volcanic
175
rock. These two potassium feldspars could be considered as two
different minerals with identical compositions but different
grain sizes. Again, the proportion of each mineral size could be
made to reflect the distribution of grain sizes, and the degree of
detail required to model the expected sampling errors can be
accommodated.
In summary, variations in mineral compositions and grain
sizes are better and more easily addressed by considering the
different compositions or grain sizes of a mineral as completely
different minerals rather than attempting to statistically in-
corporate these variations in the sampling error formula of
Equation 3.
SOFTWARE
In order to facilitate calculation of geological material sampling
errors using the approach described above, an EXCEL spread-
sheet has been prepared that makes all of the relevant calcu-
lations. This spreadsheet is flexible, in that it can easily be
expanded to consider additional minerals and additional ele-
ments. Furthermore, it not only calculates the sampling error on
every element, but estimates the geochemical composition of
the geological material under consideration, and estimates its
expected bulk density, molar mass and molar volume, given the
mineral proportions, sizes, and compositions entered by the
geologist. The program automatically calculates Poisson, bino-
mial or hypergeometric variance estimates, as requested by the
geochemist. The program also converts volume-based mineral
proportions into the mass-based mineral proportions necessary
for the calculation of the sampling error.
Readers interested in obtaining a copy of this spreadsheet
software (Sample_Size.XLS) can download it from the author’s
website at: http://ace.acadiau.ca/~cstanley/software.html.
EXAMPLE
The EXCEL spreadsheet (Sample_Size.XLS) contains the pet-
rologic information derived from a typical sample of the
Salmontail Lake Pluton, South Mountain Batholith, Nova
Scotia (Fig. 6; MacDonald & Horne 1987; Horne et al. 1989;
MacDonald et al. 1989; 1992a, b; MacDonald 2001). This
megacrystic granodiorite was sampled by the Nova Scotia Dept.
of Natural Resources during a regional lithogeochemical survey
in the late 1980’s and early 1990’s. The overall coarse grain size
and orthoclase phenocrysts make it particularly difficult to
collect representative samples of this intrusion, particularly for
some of the major oxide elements. As a result, this lithology
provides an excellent example of how the hypergeometric
sampling error calculation is made.
Samples collected as part of this reconnaissance lithogeo-
chemical survey had a sample density of c. 1 sample per 9 square
km (MacDonald et al. 1992b; MacDonald 2001), but exposure is
poor (on the order of 0.25%; pers. comm. Mike MacDonald,
NSDNR 2002). Twenty 20 kg samples were collected, and these
had a size of c. 20 cm  20 cm  20 cm (ideally 21.6 kg in
size). As a result, N/n is c. 225,000,000  0.25% = 562,500,
and the hypergeometric distribution variance formula should
thus be used for all but the most trace minerals (e.g. zircon).
Petrologic information necessary to determine the sampling
error on the major oxide analyses in the Salmontail Lake Pluton
is presented in Table 3. Information used by the spreadsheet
includes: the sample size (in g), the N/n ratio, the type of
variance to calculate (hypergeometric, binomial or Poisson), the
mineral proportions, mineral sizes (3 axis dimensions), mineral
compositions and mineral densities. Note that two potassium
feldspar minerals are used in this example to represent both the
176 C. R. Stanley

Fig. 6. Photograph of Salmontail Lake Pluton granodiorite of the South Mountain Batholith, Nova Scotia. Note megacrystic texture and
orthoclase megaphenocrysts.

Table 3. Mineral proportions, sizes and compositions of average Salmontail Lake Pluton granodiorite, South Mountain Batholith used in an example calculation of sampling error. Letters
in the ‘Distn’ column refer to the distribution used to estimate the sampling variances (H = hypergeometric; P = Poisson); numbers in the ‘Pptn’ column are the mineral proportions. Zircon
is the only mineral modeled as a nugget because all other trace minerals occur as common inclusions in biotite.

Mineral Size X (mm) Size Y (mm) Size Z (mm) Density (g/cc) Composition Distn Pptn (%)
Quartz 5 5 5 2.65 SiO2 H 32
Plagioclase 5 2 2 2.65 Na4/5Ca1/5Al6/5Si14/5O8 H 29
K-Spar Megacryst 25 10 10 2.60 K17/20Na3/20AlSi3O8 H 10
K-Spar 5 2 2 2.60 K17/20Na3/20AlSi3O8 H 12
Biotite 3 3 0.3 2.85 KAl1.4Fe1.9Mg0.9Si2.8O10(OH)2 H 11
Muscovite 0.2 0.2 0.02 2.80 KAl3Si3O10(OH)2 H 2.4
Chlorite 3 3 0.3 2.75 Mg7Fe3Al4Si6O20(OH)16 H 0.75
Andalusite 0.5 0.5 0.5 3.18 Al2SiO5 H 1.0
Garnet 0.1 0.1 0.1 4.00 Fe2MgAl2Si3O12 H 0.5
Ilmenite 0.05 0.05 0.05 4.70 FeTiO3 H 0.1
Magnetite 0.05 0.05 0.05 5.18 Fe3O4 H 0.1
Rutile 0.05 0.05 0.05 4.20 TiO2 H 0.1
Monazite 0.05 0.05 0.05 4.75 CePO4 H 0.025
Titanite 0.05 0.05 0.05 3.55 CaTiSiO5 H 0.5
Zircon 0.05 0.05 0.05 4.68 ZrSiO4 P 0.025
Apatite 0.06 0.02 0.02 2.39 Ca5(PO4)3(OH) H 0.5

phenocryst and groundmass grain sizes. Note also that zircon is
the only trace mineral modelled as a nugget because all other
trace minerals (monazite, apatite, rutile, magnetite, ilmenite, and
titanite) occur as common inclusions in biotite, and thus are
both abundant and relatively uniformly distributed in the
granite. Results from the spreadsheet calculation are presented
in Tables 4 and 5.
The sample size chosen to assess sampling error reflects that
of the survey (20 kg). However, even with this very large sample
size, the very coarse-grained rock was still sampled with
substantial error. In fact, the large sample size represented a
compromise between survey cost and representativity (Mike
MacDonald, NSDNR, pers. comm. 2002).
Note that the sampling error on K2O (1 standard deviation
relative error = 2.86%) is larger than SiO2 and Al2O3 (0.94%
and 1.16%, respectively). This is because very few orthoclase
phenocrysts are collected even in a 20 kg sample (x = 111),
producing significant sampling error in K2O, Al2O3 and SiO2.
However, because the rest of the granodiorite is mostly quartz
and plagioclase, substitution of orthoclase for quartz or plagi-
oclase replaces the SiO2 in orthoclase with SiO2 in quartz and
plagioclase, and replaces the Al2O3 in orthoclase with Al2O3 in
 Sample errors for elements in geological materials 177

Table 4. Results of example calculation of sampling error for Salmontail Lake Pluton granodiorite, South Mountain Batholith for 20 kg sample and N/n = 562 500. The various numbers
of target mineral equant grains (x), total equant grains (n), error on the number of target equant grains (
x), and wt. % errors and relative errors on target mineral abundances are presented.
Note that a large number of target mineral grains occur, except for the K-spar megacrysts, in a 20 kg sample.

Mineral # of equant, target mineral grains Total # of equant grains (n) Sampling error on # of mineral Mineral wt. % error Mineral relative wt. % error
(x) grains (
x)
Quartz 7.09103 2.2104 69 0.309 0.980
Plagioclase 4.01104 1.38105 169 0.120 0.421
K-Spar Megacryst 1.11102 1.11103 10 0.872 9.015
K-Spar 1.66104 1.38105 121 0.084 0.728
Biotite 1.13105 1.03106 317 0.0328 0.281
Muscovite 8.31107 3.46109 9,003 0.000271 0.011
Chlorite 7.69103 1.03106 87 0.00872 1.136
Andalusite 1.38104 2.77106 117 0.00631 0.848
Garnet 2.21107 2.211010 4,704 0.000037 0.021
Ilmenite 2.21107 2.211010 4,704 0.000041 0.021
Magnetite 2.21107 2.211010 4,704 0.000033 0.021
Rutile 5.54106 2.211010 2,353 0.000019 0.042
Monazite 1.11107 2.211010 10,497 0.000063 0.009
Titanite 5.54106 2.211010 2,353 0.000018 0.042
Zircon 5.77107 1.151011 23,956 0.000018 0.004
Apatite 7.09107 2.21104 69 0.309 0.980

Table 5. Results of example calculation of sampling error for Salmontail Lake Pluton granodiorite, South Mountain Batholith for 20 kg sample and N/n = 562,500. The bulk density
of the rock is 2.69 g/ml, its bulk molar volume is 49.03 ml/mole, and its bulk molar mass is 131.78 g/mole. The calculated volume for a 20 kg sample is 7,441 ml.

Element Element Composition (wt. %) 1 SD Sampling Error on Element Composition 1 SD Relative Sampling Error on Element
(wt. %) Composition (CV%)

SiO2 69.771 0.655 0.939

TiO2 0.517 0.000046 0.009
Al2O3 14.147 0.164 1.161
Fe2O3 0.133 0.000028 0.021
FeO 3.708 0.00934 0.252
MgO 1.079 0.00306 0.284
CaO 1.641 0.00508 0.310
Na2O 3.048 0.0185 0.609
K2O 4.452 0.127 2.856
P2O5 1.245 0.00302 0.243
H2 O 0.193 0.000008 0.004
Zr (ppm) 215 0.088 0.042
Ce (ppm) 307 0.128 0.042

plagioclase. As a result, the sampling errors for SiO2 are lower
than the sampling errors for Al2O3, and both of these are
substantially lower than the sampling errors for K2O.
All other elements exhibit less than 1% relative error, largely
because they occur in minerals that have large numbers of
grains in the sample.
CONCLUSIONS
The propagation of variance approach allows determination of
sampling errors for major, minor and trace elements in geologi-
cal materials. The approach first estimates the sampling error
for each mineral in a geological material using the equant grain
model, and then propagates this variance into sampling error on
the elements in the sample. The approach is flexible, as it
employs several statistical distributions to deal with rare and
common grain sampling errors. Furthermore, it is statistically
valid, and requires no simplifying assumptions about mineral
sizes, mineral compositions, or how many minerals contain an
element. The propagation of variance approach to sampling
error estimation can be used to estimate the magnitude of
sampling error in geological materials using only information
that can be readily obtained by simple hand sample or thin
section inspection.
This research was supported by an NSERC discovery grant to the
author. It benefited from a number of philosophical discussions years
ago about sampling errors with Dr. Alastair Sinclair, and from more
recent discussions with Dr. Paul Cabilio (Acadia University), and
Dr. Mike MacDonald and Ms. Linda Ham (NSDNR).
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