The use of duplicates, Thompson and Howarth method, on evaluation of

sampling protocol, Cuiabá mine, Brazil

Andrade, V. R.1; Villanova, F. L. S. P.2; Canela, J. H. C.2
1
Federal University of Minas Gerais, Brazil
2
AngloGold Ashanti, Sabará MG, Brazil

Duplicate samples are a requirement from resource definition to mining operation, for any code
reporting investment. The duplicates usually consist of assayed pulp which is re-labelled and re-
submitted to the laboratory. The use of duplicates on quality assurance and quality control is well
known mostly to test the assay repeatability of each sample type, i.e. rig, crushed and pulp.
Consequently, duplicates can monitor the variance in the sub-sampling processes and identify sample
swops and carry-over contamination. However they can also be used to qualitatively evaluate sampling
protocols. Thompson and Howarth (1976) presented a straightforward alternative to evaluate
imprecision of sampling protocol using duplicates. It is a simple method that estimates graphically and
quantitatively, the coefficient of variation or the imprecision of paired data. In January of 2018, a change
on the protocol occurred in Cuiaba gold mine, Brazil, due to a crusher upgrade, which reduced the
crushed material to be pulverized. To evaluate this change, the duplicate analysis suggested by
Thompson and Howarth (1976) is used in this study, to both crushed and pulp duplicates. From this,
based on the last two years historical data, it is possible to determine whether or not the change of
protocol is suitable, according to the lithology, mineralization style (gold associated with sulfides or gold
free in quartz) and gold grain size. When the imprecisions of crushed e pulp duplicates are compared, is
expected the later to be superior compared to crushed imprecision. The opposite suggested the
presence of coarse gold grains, which increases the variability. The mass of the actual protocol is
adequate for lithologies with gold associated with sulfides, but as expected, the mass proved to be
insufficient when gold was free in quartz.

1. Introduction

Random sampling errors result on erroneous decisions regarding to the selection of

ore and waste. This, in its turn, can take to reconciliation errors and error on production
calculation. These errors must be identified and reduced to an acceptable and controlled level.
One of the ways to do this is by regular duplicate sampling on each sampling stage.

Duplicate samples are a requirement from resource definition to mining operation, for
any code reporting investment. The duplicates usually consist of assayed pulp which is re-
labelled and re-submitted to the laboratory. The use of duplicates on quality assurance and
quality control is well known mostly to test the assay repeatability of each sample type, i.e. rig,
crushed and pulp. Consequently, duplicates can monitor the variance in the sub-sampling
processes and identify sample swops and carry-over contamination. However they can also be
used to qualitatively evaluate sampling protocols.

The Australasian Joint Ore Reserves Committee (JORC), the National Instrument (NI-
43/101) from Canada and the South African Code (SAMREC ) are the most known codes that
regulate the public reports of mining companies, Mineral Exploration Results, Mineral
Resources and Ore Reserves; assuring a level of confidence. JORC in terms of “quality of assay
data and laboratory tests” criteria determines that “the QA/QC program includes CRMs,
blanks, preparation duplicates and field duplicates and is acceptable according to industry
standards.”. SAMREC code states that for QA/QC it is necessary to “Demonstrate that
adequate field sampling process verification techniques (QA/QC) have been applied, e.g. the
level of duplicates, blanks, reference material standards, process audits, analysis, etc.”

AngloGold Ashanti has an internal document providing QAQC guidelines that declares
the general Quality Assurance (QA) and Quality Control (QC) requirements for all assay
practices and subsequent processes used for Metal Accounting purposes. This document has
the SAMREC CODE as one of its references. The following table informs the percentage of
samples that must be analyzed according to the guideline for mine geology samples (grade
control and Measured resources) (Table 1).

Table 1 - Minimum of QAQC samples that must be put in sample batchs. The red rectangle
highlights phases of Mine Geology.

The sampling protocol applied to core drill samples and channel samples on the AGA’s
laboratory, until the moment of acquisition of Boyd crusher machine (December 2017), can be
summarized according to the following stages:

1) drying the sample at 110 ° C;

2) material crushing - 90% less than 2.0 mm;

3) reduction of the mass of the primary sample to 500 g with the use of a Jones
splitter;

4) pulverization in a pulverizing mill - 80% less than 75 μm;

5) selection of a 30 g aliquot (using a spatula) for fire assay analysis, with gold
determination by atomic absorption spectroscopy (AAS) or gravimetric finish.

The actual protocol is:

1) drying the sample at 110 ° C;

2) material crushing - 90% less than 3.175 mm;

3) sample mass split to 300 g, by a rotatory splitter coupled on the crusher;

4) pulverization in a pulverizing mill - 90% less than 75 μm;

 5) selection of a 30 g aliquot (using a spatula) for fire assay analysis, with gold
determination by atomic absorption spectroscopy (AAS) or gravimetric finish.

In both protocols, the materials that are not selected on stages 3 and 5 of mass
reduction are named crusher residue and pulp residue, respectively. These samples can be
archived for further analysis.

This paper aims to understand the variability of each lithotype in sampling stages, as
well as to verify the possible impact of sampling protocol change, mainly of the most variable
litologies.

Geological setting:

Iron Quadrangle (IQ) is a worldwide known metalogenetic province for its gold and
iron deposits, located in Minas Gerais, Brazil. Cuiabá mine is a suphide-hosted gold deposit
very known for its grade and ton, located on the north border of IQ.

Cuiaba mine rocks comprises rocks of Nova Lima Group, Rio das Velhas Supergroup, an
Archean greenstone belt sequence (Dorr, 1969). It is within the volcanoclastic association of
Baltazar and Zucchetti (2007), part of a matavolcano-sedimentary sequence. The deposit is a
lithological succession of metavolcanic, metavolcanoclastic and metasedimentary rocks. The
basal unit is metandesite with intercalated phyllites, overlaid by chemical-sedimentary rocks
(banded iron formation and ferruginous chert). Above this unit there are carbonaceous phyllite
and metabasalt with intercalated micaceous phyllite, overlaid by a unit composed by
micaceous phyllite and metavolcanoclastics rocks (Vial, 1980).

The mineralization is structurally controlled and the major orebodies are hosted on
banded-iron formation (BIF) and ferruginous chert. The mineralization is directly related to
hydrothermal alteration and gold occurs associated and included in sulphides (pyrite,
pyrrothite and arsenopyrite) in the BIF and in venulated sulphide schists (XS). Gold also occurs
free in quartz veins (QZ) that cross-cut metabasalts and metassediments, and can be fine
grained (10 micrometers) to coarse (1 millimeter).

Table 2 summarizes the lithologies that host the mineralization and were analyzed in
this study.
Table 2 – Logged lithotypes in Cuiabá mine.
Lithotype Acronyms Description
Rock with alternating layers of dark quartz-
carbonate-carbonaceous matter and translucent to
Banded-iron formation BIF orange quartz-carbonate-chert bands. Visually
estimation of a maximum of 5% of sulphides along
the bands.
Banded-iron formation with more than 5% of
Massive sulphide S
sulphides (pyrite or pyrrhotite).
Beige rocks intensely veined with quartz and
carbonate, showing a penetrative mylonitic
foliation. Resulted from hydrothermal alteration of
Sulphide schist XS
metavolcanoclastic rocks, mostly on the proximal
zone (sericite). Disseminated pyrite and/or
pyrrhotite are common.
Quartz veins QZ Veins composed by smoky and/or white quartz,
 sometimes with associated carbonates and sericite
and chlorite-rich films. Sulphides can occur as
accessory minerals and free gold can be observed
macroscopically if it is coarse-grained.

The main orebodies in production are: Fonte Grande, Serrotinho, Balancão and
Galinheiro. Figure 1 is a geological map of level 11 of the Cuiabá mine, showing the main
orebodies and mineralized zones.

Figure 1 - Geological map of Level 11 of the Cuiabá mine showing the main orebodies associated with
BIF (FGS – Fonte Grande Sul, SER – Serrotinho, BAL – Balancão, GAL – Galinheiro, GAL EXT – Galinheiro
extensão, DDO – Dom Domingos, CGA – Canta Galo, SUR – Surucu), and mineralized zones related to
quartz-carbonate veins (VQZ, SER FW – Serrotinho Footwall, FGS FW – Fonte Grande Footwall) (Vitorino,
2017).

2. Methodology

In this paper, for the application of Thompson and Howarth (1976) method, two years
historical data available is grouped with regards to the orebody and the lithology, according to
Table 3. First of all, to use this method it is necessary a minimum of 50 pairs of data (original
sample and duplicate) and the groups with less than this were ignored.

The Thompson & Howarth (1976) method applied in this study can be summarized as
follows:

 From de duplicate list, calculate the mean e absolute difference of the pairs
(original sample and duplicate);
 Organize the data in increasing order considering the mean values;
 From the first 11 results of the list, calculate the concentration mean value and
the median of the absolute difference values;
  Repeat the previous procedure to each successive group of 11 samples,
ignoring those that left and are less than 11 in total;
 Complete the linear regression of median values on mean values.

The variation coefficient of all batch used for the regression is approximately the graph
inclination. The graph intercept is the detection limit, once it should be related to the standard
deviation (in this case de median) of the system measured at or near zero concentration value
(Thompson & Howarth, 1976). According to Carsweel et al (2009), the imprecision is twice the
variation coefficient.

3. T-H Plot

Thompson and Howarth method is described in Methodology. This is method was

chosen for this study because it is a straightforward alternative to evaluate imprecision of
sampling protocol using duplicates. It is a simple method that estimates graphically and
quantitatively, the coefficient of variation or the imprecision of paired data.

Any sampling stage, which means, mass reduction, results on errors (sample collection,
in case of channel samples, quartering of crusher or pulp fragments and selection of the
reduced sample). A duplicate collected in one of these stages will show the errors of post
stages, however it is not possible to determine in which of this phases this error occurred. In
this way, the comparison of two stages duplicates, theses stages consecutive, allows possible
errors to be identified. For example, the crusher duplicate contemplates an error that could
have occurred on crushing phase, associated to ideal top size and/or the mass, or that could
have occurred on the following stages of subsampling. Pulp duplicates, on the other hand,
indicates errors that occurred during pulverization, also associated to ideal top size or mass
and the following stage, and during the selection of the final analytical aliquot.

Comparisons between error values associated to crushed and pulp duplicates can bring
understanding from protocol adequacy to mineralization types. It is expected an imprecision
reduction all throughout sampling stages, from collection to analysis, and any inconsistency on
this reduction is intrinsically related to gold particles size and to top size and/or masses
considered on the protocol. However, even using these comparisons, it is not viable to be
certain if the imprecision is due to the sample mass or top size.

Pierre Gy was a pioneer creating the Theory of Sampling (TOS) to address sampling
problems related to the size of the samples. His well know formula (Gy’s equation) is applied
to predict, estimate or minimize the variance of the “Fundamental Sampling Error” (FSE).

This variance, VarGy(FSE), is related to a sampling error resulted from representing a

lot by an aliquot (Gy, 1979, 1988), and is defined as:
( ) ⁄

where ( ) is the prediction made by Gy’s TOS for Var(FSE), is particle shape factor, g
is size range factor of the particles in the population, is liberation factor of the particles in the
population, is mineralogical composition factor of the particles in the population, is
material top-size, and is the mass (or weight) of a sample (Gy, 1979).

The understanding of Gy’s formula is of the utmost importance for suggesting changes
based on the T-H plot method. As noted on this equation, any change on the top-size produces
significant changes on the variance of the error. However, this is often limited to the
equipment available. Therefore, another way of reducing the error is by increasing the mass of
the sample, which could also be a bottle neck, but could be more viable.

4. Results

Data from Balancão, Fonte Grande, Serrotinho, Galinheiro e VQZ orebodies of Cuiaba
mine was analyzed. The information is divided according to the lithotypes: iron banded
formation (BIF), massive sulfide (S), sulphide schist (XS) and quartz veins (QZ). For each of
these lithotypes, crushed (DCR1) and pulp (DP1) duplicates data are available. Table 3
summarizes available dada.

Table 3 – Duplicate data available for this study. The data with 5 or more groups, in which T-H method
was applied, is highlighted in green.
Number of Number of groups
Orebody Lithology Top size
duplicates (11 paired data in each)
DP1 4 0
BIF
DCR1 2 0
DP1 26 2
S
DCR1 1 0
BALANCÃO
DP1 13 1
XS
DCR1 11 1
DP1 57 5
QZ
DCR1 14 1
DP1 134 12
BIF
DCR1 78 7
DP1 56 5
S
DCR1 10 0
FONTE GRANDE
DP1 30 2
XS
DCR1 11 1
DP1 65 5
QZ
DCR1 20 1
DP1 116 10
BIF
DCR1 44 4
DP1 49 4
S
DCR1 12 1
GALINHEIRO
DP1 46 4
XS
DCR1 24 2
DP1 124 11
QZ
DCR1 60 5
DP1 69 6
BIF
DCR1 38 3
DP1 36 3
S
DCR1 18 1
SERROTINHO
DP1 43 3
XS
DCR1 11 1
DP1 82 7
QZ
DCR1 30 2
DP1 n.a. -
BIF
DCR1 n.a. -
DP1 n.a. -
S
DCR1 n.a. -
VQZ
DP1 9 0
XS
DCR1 6 0
DP1 53 4
QZ
DCR1 29 2
 According to the method proposed, only the groups that comprise 55 or more pairs of
duplicates should be considered. Linear regressions of median values over mean values for
data that fits this requirement are presented on Figure 2.

T-H Plot Fonte Grande_BIF_DCR1 DH Grouped data T-H Plot Fonte Grande_BIF_DP1 DH Grouped data

0.9 1.2
Group Median Absolute Difference (g/t)

Group Median Absolute Difference (g/t)

N = 66 N = 132
0.8 Imp. = 15% Imp. = 24,5%
1
0.7
0.6 0.8
0.5
0.6
0.4
0.3 y = 0.0757x + 0.0209 0.4 y = 0.123x + 0.0399
0.2 R² = 0.9904 R² = 0.923
0.2
0.1
0 0
0 5 10 15 0 2 4 6 8 10
Group Mean Gold Grade (g/t) Group Mean Gold Grade (g/t)

T-H Plot Fonte Grande_S_DP1 DH Grouped data T-H Plot Fonte Grande_QZ_DP1 DH Grouped data

3.5 16
N = 55 N = 55
Group Median Absolute Difference (g/t)

Group Median Absolute Difference (g/t)

3 Imp. = 10.8% 14 Imp. = 107.7%

2.5 12
10
2
8
1.5
y = 0.0538x + 0.7293 6 y = 0.5384x - 0.1252
1
R² = 0.6886 4 R² = 0.9993
0.5 2
0 0
0 10 20 30 40 50
-2 0 10 20 30
Group Mean Gold Grade (g/t) Group Mean Gold Grade (g/t)

T-H Plot Galinheiro_BIF_DP1 DH Grouped data T-H Plot Galinheiro_QZ_DCR1 DH Grouped data

0.25 0.7
Group Median Absolute Difference (g/t)

Group Median Absolute Difference (g/t)

N = 110 N = 55
Imp. = 8.5% 0.6 Imp. = 38%
0.2
0.5
0.15 0.4

0.1 0.3
y = 0.0425x + 0.0465 y = 0.1886x + 0.0422
R² = 0.3916 0.2 R² = 0.981
0.05
0.1
0 0
0 1 2 3 4 5 0 1 2 3 4
Group Mean Gold Grade (g/t) Group Mean Gold Grade (g/t)
 T-H Plot Galinheiro_QZ_DP1 DH Grouped data T-H Plot Serrotinho_BIF_DP1 DH Grouped data

1.4 0.2
N = 176 N = 66

Group Median Absolute Difference (g/t)

Group Median Absolute Difference (g/t)
1.2 Imp. = 42% Imp. = 2.4%
1 0.15

0.8
0.1
0.6 y = 0.012x + 0.0643
y = 0.2106x + 0.0346 R² = 0.2429
0.4 0.05
R² = 0.976
0.2
0 0
0 2 4 6 8 0 2 4 6 8 10
Group Mean Gold Grade (g/t) Group Mean Gold Grade (g/t)

T-H Plot Serrotinho_QZ_DP1 DH Grouped data

1.4
Group Median Absolute Difference (g/t)

N = 77
1.2 Imp. = 32%

1
0.8
0.6
0.4 y = 0.1602x - 0.0346
0.2 R² = 0.9465

0
0 2 4 6 8
-0.2
Group Mean Gold Grade (g/t)

Figure 2 – T-H plots of lithotypes of Fonte Grande, Galinheiro and Serrotinho orebodies.

5. Discussions

The TH plots can be discussed in terms of imprecision: for the same lithotype and orebody,
observe the difference in imprecision for pulp and crushed duplicates; difference in
imprecision of different lithotypes; comparision of the imprecision of a lithotype in different
orebodies. The limitation of available data for this study causes some of these correlations not
possible to be addressed. In terms of comparison between imprecision of crushed and pulp
duplicates, it is expected an inferior value of the latter, compared to the imprecision of
crushed duplicates of the same lithology, and these values can bring discussions in terms of
gold grain size. Another discussion that can be brought observing T-H plots is with respect to
the detection limit, as the graph intersection is the detection limit. Moreover, throughout the
distribution profile of the samples, is possible to argue with relation to mineralization
continuity.

Balancão and VQZ orebodies do not have sufficient duplicate data to be analyzed
according the T-H plot method, used in this paper. Therefore, only plots of some lithotypes of
Fonte Grande, Galinheiro and VQZ were further discussed.

Comparing the imprecision on BIF pulp duplicates, samples from Fonte Grande have
the higher imprecision of 24.5%, whereas Galinheiro and Serrotinho have much lower values
of 8.5% and 2.4% respectively. A noteworthy point for Fonte Grande is that the orebody is cut
by a fault with divides it in half. The South side, being associated with sulphides and the North
side associated with a high degree of BIF silicification. The gold bearing quartz alteration on BIF
is related to an increase of gravimetric recovery seen at the plant, when this ore body is mined.
The presence of free gold is marked by an increase on variability of the duplicates.

For QZ lithotype, pulp duplicates of Fonte Grande oreboby pointed an imprecision of

107.7% and 42% for Galinheiro. The high value of Fonte Grande QZ, can also be explained by
the peculiarity of the mineralization on each side of the fault.

The only sufficient duplicate data available for S is of Fonte Grande oreboby, and a
value of 10.8% of imprecision was found. For this orebody, because of structural aspects
pointed above, the meaning of this value is not explicit. Even though the imprecision value can
be considered acceptable, the value of 0.7 of intercept, is noticeable greater than the
detection limit (0.05). However, it is important to observe that there is a dispersion of the data
along the regression line (R2=0.68), and this can result on a bad inference of the detection
limit, which means that certainly it is not near 0.05, but also not 0.7. Since the lithotype is
massive sulfide, that is generally easy to be sampled, a high value of detection limit can
indicate coarse gold grains (associated to sulphides), which are easily released during the
milling process.

For BIF lithotype of Fonte Grande orebody, it is possible to compare the imprecision of
crushed and pulp duplicates. The former is 15% and the latter is 24.4%. As it is expected an
inferior value of imprecision on pulp duplicates, the opposite suggests the presence of coarse
gold grains, which increases variability when gold is released. Less expressively, this fact was
also observed in Galinheiro quartz vein (QZ) lithotype, for which T-H plot showed an
imprecision of 38% for crushed duplicates and of 42% for pulp duplicates.

T-H plots can be discussed in terms of the distribution profile of the samples. The
discontinuous nature of the plotted points indicates an erratic mineralization, most commonly
associated with free gold. This was strongly observed for QZ duplicates of Fonte Grande and
Serrotinho. T-H plots with a more continuous distribution along the line (pulp duplicates of
Galinheiro QZ and Fonte Grande BIF) indicate a more homogeneous mineralization, in which a
higher grade is attributed to a higher concentration of sulfides.

According to the plant requirements, fit-for-purpose imprecision values suggested are

of a maximum of 15% for pulp duplicates and 30% for crushed. For all the lithotypes in which a
high value of imprecision was observed the easier manner of suiting the protocol is by
increasing the mass to be pulverized. If, from this, the value of imprecision is still high, the
analytical mass could be increased, and two or three analysis could be done. The value
considered would be the mean value.

6. Conclusions

Mass reduction for lithotypes that have shown high values of imprecision leads to an increase
on variance, resulting on an even greater imprecision. Mainly for lithotypes with coarse gold
grains, prone to generate a nugget effect, a mass reduction on the protocol is not suitable.
Instead, an increase on the mass would be suggested.
For lithotypes with fine gold grains or associated with sulphides, the mass reduction would not
impact that much on the value of imprecision. However, this might be experimentally checked.

It is suggested the sampling protocol to be changed, focusing on samples with grade at least 10
times the detection limit, because high grades defines the ore and consequently, should define
the sampling protocol. Low grades tend to be less erratic, possibly due to fine gold (free gold
sulphide associated or microscopic) that is easily sampled.

For the results to be analyzed again, a minimum of 55 duplicates of each lithotype and
orebody are requested, and this will take a while in order to use data exclusively of the actual
protocol. When a sufficient number of duplicates are available, will be possible to compare the
results of both protocols and come up with proposals of suiting it.

7. References

Baltazar, O.F., Zucchetti, M., 2007. Lithofacies associations and structural evolution of the
Archean Rio das Velhas greenstone belt, Quadrilátero Ferrífero, Brazil: a review of the
setting of gold deposits. Ore Geol. Rev. 32, 471–499.

Carswell, J. T., Yulia, K., Lesmana, D., & Steamy, K., 2009. Grade control sampling quality
assurance/quality control in a high-grade gold mine—Gosowong, Indonesia.
In Proceedings of the 7th International Mining Geology Conference (pp. 283-290).
Melbourne. The Australasian Institute of Mining and Metallurgy.

Dorr, J.V.N., 1969. Physiographic, Stratigraphic and Structural Development of the

Quadrilátero Ferrífero, Minas Gerais, Brazil. Regional Geology of the Quadrilátero
Ferrífero, Minas Gerais, Brazil.

Gy, P., 1979. Sampling of Particulate Materials. Theory and Practice. Elsevier, Amsterdam. 431
pp.

Thompson, M and Howarth, R J, 1976. Duplicate analysis in geochemical practice part 1:

Theoretical approach and estimation of analytical reproducibility, Analyst, 101:690-
698.

Vial, D.S., 1980. Mapeamento Geologico do Nivel 3 da mina de Cuiabá, Mineração Morro Velho
as: Internal Report.

Vitorino, A.L.A., 2017. Mineralização aurífera associada aos veios quartzo-carbonáticos

hospedados na unidade máfica basal da jazida Cuiabá, greenstone belt Rio das Velhas,
Quadrilátero Ferrífero, Minas Gerais, Brasil.

Vanessa Resende de Andrade

Geologist
Vanessa is a Geologist graduated in Federal University of Minas Gerais,
Brazil, in July 2018, when she also finish, after 18 months, an internship in
AngloGold Ashanti company, at Lamego and Cuiaba mines. With the
experience at AngloGold Ashanti and an international experience of 15
months of exchange in Australia, she is currently looking for a position as
junior geologist or trainee.