Journal of Geochemical Exploration 73 (2001) 1±10

www.elsevier.nl/locate/jgeoexp

Soil geochemical prospecting for gold at Marrancos

(Northern Portugual)
A.P. Reis a,b,*, A.J. Sousa a, E. Cardoso Fonseca c
a
Bolseira Programa Praxis XXI, Portugal
b
CVRM, Instituto Superior TeÂcnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
c
Departamento de GeocieÃncias, Universidade de Aveiro, 3810 Aveiro, Portugal
Accepted 19 April 2001

Abstract
This paper discusses some geochemical mapping techniques and their effectiveness in detecting of gold and its path®nder's
geochemical anomalies. The study area (Marrancos area) is situated in Northern Portugal. Gold occurs in a quartz breccia with
pyrite and arsenopyrite hosted by metamorphic rocks (hornfels) and it is present in these two sulphide minerals as inclusions or
disseminated in the crystal lattice. In this area, the geochemical anomalies obtained by isoconcentration mapping of single
elements were dif®cult to interpret. The use of alternative geochemical mapping such as multielement halos (additive halos)
proved to be effective in the de®nition of Au, As, Bi, Sb, Te and Se secondary geochemical signature. q 2001 Elsevier Science
B.V. All rights reserved.
Keywords: gold; path®nder elements; geochemical halos; soil geochemistry; Portugal

1. Introduction Nichol et al., 1989). A common way of overcoming

Gold is well known as a relatively immobile element
in the super®cial environment. Consequently, the
geochemical super®cial signature of a gold occurrence
is often limited and dif®cult to interpret. However, under
certain physical and chemical conditions, epigenetic
gold may become mobile and disperse from its source
to form geochemical gold anomalies at the surface.
Since gold forms malleable particles and is
highly resistant to comminution, it normally gives a
poor sample representativity and poor analytical
reproducibility (Clifton et al., 1969; Harris, 1982;
* Corresponding author. Address: CVRM, Instituto Superior
TeÂcnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. Tel.:
1351-234-370804; fax: 1351-234-370605.
E-mail address: pmarinho@geo.ua.pt (A.P. Reis).
0375-6742/01/$ - see front matter q 2001 Elsevier Science B.V. All rights reserved.
PII: S 0375-674 2(01)00169-8
this problem has been to use large samples for analy-
sis, a procedure that has turned out to be impractical in
many cases. Another way of eliminating the in¯uence
of coarse particulate gold and improving sample
representativity and analytical reproducibility is the
use of ®ne fractions of soil (Salpeteur and Sabir,
1989; Xie and Wang, 1991; Sibbick and Fletcher,
1993; Wang et al., 1995)
In Portugal, the ,80 mesh fraction is commonly
used in geochemical prospecting for gold. Studies of
gold distribution in the soil size fractions have not
been performed in Portugal. Nevertheless, an orienta-
tion survey recently done in the Marrancos area has
shown that the ,200 mesh fraction is most suitable
for geochemical prospecting of gold (Reis et al., 1993/
94). The study also identi®ed the path®nder elements
for gold and the most suitable analytical procedures.
2 A.P. Reis et al. / Journal of Geochemical Exploration 73 (2001) 1±10
Fig. 1. Geological map, modi®ed (Medeiros et al., 1974).
This paper discusses the applicability of several
methods of enhancing super®cial halos for gold and
its path®nders in Marrancos mineralisation.
2. Geology and mineralisation
The study area is located in Northern Portugal (Fig.
1). The mineralisation occurs in a NE±SW late-
Hercynian sub-vertical breccia within Silurian meta-
sediments adjacent to a Hercynian granitoid (Fig. 1).
The quartz breccia is located in a hornfels zone
developed at the schist/granitoid contact (Medeiros et
al., 1974) and is spatially related to a major shear zone,
the WNW±ESE Vigo±ReÂgua shear zone (Medeiros et
al., 1974). Macroscopically the hornfels is divided into
®ne-grained biotite/muscovite hornfels and banded
coarse-grained quartz-feldspar hornfels. Small quartz-
sulphide veins frequently crosscut the metasediments.
In the Marrancos mineralisation (34.8 g/ton maxi-
mum value for gold), gold occurs mostly in the form
of electrum which is hosted by sulphide minerals such
as arsenopyrite and pyrite as small inclusions or dis-
seminated in their crystal lattice (Reis, 1997).
An Fe 1 As 1 Bi 1 Au 1 Sb 1 Se 1 Te 1 …Pb 1
Ag† assemblage de®nes the primary geochemical
signature of the Marrancos mineralisation, which
has correspondence in a mineralogical assem-
blage of arsenopyrite 1 pyrite 1 bismuthinite 1 gold/
electrum 1 (galena) with minor chalcopyrite and
sphalerite (Noronha and Ramos, 1993; Reis, 1997).
Silver does not occur in the native state but is
contained in sulphide minerals, commonly galena.
Antimony, Te and Se do not form their own minerals
and are hosted by sulphides.
Supergene weathering of the outcropping quartz
breccia has produced scorodite, pyrrhotite and
secondary Fe-oxides (goethite, hematite) at the
surface (Reis, 1997). Microprobe analysis of these
weathering products has shown that scorodite, Fe-
oxides and pyrrhotite have signi®cant contents of
gold in the structure (Reis et al., 1997).
The soil developed in the area is a brown soil type
(Carvalho Cardoso et al., 1971), with a low content in
organic matter and a medium to coarse grain size. The
soil varies in depth from 10 to 30 cm. The vegetation is
not abundant (pine trees and eucalyptus). A maritime
temperate climate prevails in the area with a mean
annual rainfall of above 1500 mm and an average
temperature of 15±168C. The topography of the area
is smooth and consists in a small hill with a gentle slope.
3. Methods
3.1. Sampling and sample preparation
The soil samples were collected in a rectilinear grid
 A.P. Reis et al. / Journal of Geochemical Exploration 73 (2001) 1±10
at equal distances (40 m) along evenly spaced lines
(50 m). The lines are oriented perpendicularly to the
NE±SW trending quartz breccia (Fig. 1).
The samples, collected at 10±30 cm depth, were
dried at a temperature of 508C for 24 h. The ,200
mesh fraction obtained by dry sieving was retained
for chemical analysis.
3.2. Chemical analysis
The 286 soil samples were analysed for Fe, Cu, Zn,
Pb, Co, Ni, Mn, Ag and Bi by atomic absorption
spectrometry (AAS). An aqua regia attack was used
for Ag and Bi (Ward et al., 1969) while a hot HCl±
HNO3 ±HF attack was used for the remaining
elements (Lecomte and Sondag, 1980). Bismuth was
the only chemical element with concentrations below
the 0.2 ppm detection limit of the analytical method.
All values of Fe, Cu, Zn, Pb, Co, Ni, Mn and Ag are
above the detection limit of the analytical methods
(detection limit: Cu, Zn, Pb, Co, Ni, Mn and Ag Ð
0.1 ppm; Fe Ð 1.0 ppm).
Arsenic, Sb, Se and Te were analysed by atomic
absorption spectrometry Ð hydride generation (AAS-
HG; Varian Techtron, 1984) following a HClO4 ±HF
attack (Aslin, 1976) with detection limits of 5 ppb for
As, Sb, Se and Te.
The analytical method used for gold required 10 g
of soil sample. An HCl/HNO3 mixture dissolved the
gold, with a previous addition of H2O2 in order to
liberate gold attached to organic matter. The metal
was then extracted from the solution by an organic
solvent, methyl-isobutylketone (MIBK), and the
organic phase was analysed by Inductively Coupled
Plasma Ð Atomic Emission Spectroscopy (ICP-
AES) (Reis et al., 1993/94) with a detection limit of
7 ppb Au.
The precision of the analytical results is based on
the routine replicate sampling (30 duplicates) accord-
ing to the method described by Garrett (1969, 1973).
Values for precision are: ^14% for Fe, ^4% for Cu,
^5% for Zn, ^6% for Pb; ^6% for Co, ^4% for Ni
and ^5% for Mn. The precision for the remaining
chemical elements was estimated to be around ^9%
for As, ^19% for Sb, ^14% for Te, ^10% for Se,
^8% for Ag, ^12% for Bi and ^22% for Au.
The analytical precision for gold is lower than for
the other elements, probably due to a heterogeneous
3
distribution of gold in the soil samples (nugget effect)
in combination with the small amounts of metal in the
MIBK extract.
4. Results
In order to enhance the super®cial geochemical
signature of gold and its path®nders, a comparative
study was undertaken using different mapping tech-
niques such as the isoconcentration monoelement
mapping and the multielement halos techniques.
The chemical elements strongly correlated with
gold in Marrancos mineralisation such as As, Bi, Sb,
Te and Se are those studied in this paper.
4.1. Basic statistics of the variables
Table 1 contains some summary statistics for the 14
variables. As indicated by their skewness coef®cients
(for raw data) all distributions are positively skewed.
Some maximum values are very large, over nine or ten
standard deviations from the mean (As, Cu, Se, Ag, Bi
and Fe). Such values, however extreme, should not be
discarded since some of the most interesting (As, Se,
Ag and Bi) anomalies would probably be discarded
with them.
Therefore, the decision was made to work with the
decimal logarithmic of the data instead of the raw
values, which very effectively reduces the asymmetry
of the distribution as testi®ed by the skewness coef®-
cient (log). All the methods studied in this paper rely
upon the logarithmic transformation of raw data from
Marrancos area.
4.2. Single element mapping
The graphical method of determining statistical
parameters from cumulative probability graphs
assumes that the population is homogeneous, nor-
mally or lognormally distributed and mono or poly-
modal (Lepeltier, 1969). In this study, based on the
probability density functions, lognormal distributions
were assumed for all data populations.
Fig. 2 presents the histograms and the probability
plots of Au, As and Bi, the most important elements
in the Marrancos mineralisation, representing the
three different types of data distributions. In the
case of unimodal-low values trend populations like
4 A.P. Reis et al. / Journal of Geochemical Exploration 73 (2001) 1±10

Table 1
Basic statistics of the variables. The logarithmic transformation is effective in reducing the asymmetry of the distributions

Elements Mean SD Min. Max. Skewness Mean (log) SD (log) Skewness (log)

As (ppm) 768 2077 18 19950 6.4 2.35 0.62 0.7

Au (ppb) 147 554 7 4940 6.9 1.49 0.63 1.1
Mn (ppm) 603 264 185 1324 0.6 2.74 0.20 20.2
Cu (ppm) 48 18 26 205 4.9 1.66 0.12 1.7
Zn (ppm) 112 37 35 262 0.9 2.03 0.14 20.2
Pb (ppm) 65 23 19 193 1.8 1.79 0.14 0.4
Sb (ppb) 96 125 5 831 2.7 1.66 0.57 20.2
Se (ppb) 17 32 5 309 4.7 0.94 0.42 1.6
Te (ppb) 48 40 5 294 2.6 1.56 0.33 20.3
Co (ppm) 39 7 20 63 0.3 1.58 0.09 20.4
Ni (ppm) 72 15 43 116 0.4 1.85 0.09 20.2
Ag (ppm) 0.8 0.3 0.4 4 6.5 20.12 0.11 2.0
Bi (ppm) 4.0 13.3 0.2 140 7.7 20.04 0.68 0.7
Fe % 4.98 1.10 2.97 13.71 2.1 0.69 0.09 0.5

Fig. 2. Probability plots and histograms for Au, As and Bi data populations (lognormal distributions).
 A.P. Reis et al. / Journal of Geochemical Exploration 73 (2001) 1±10 5

Table 2 1969) are narrow and restricted to the mineralised

Statistical parameters calculated for gold and its path®nder elements quartz breccia location. Consequently, they character-
(lognormal distributions) (As and Bi data in ppm; Au, Sb, Te and Se
data in ppb)
ise poorly the super®cial signature produced by the
mineral deposit.
Elements P50% P84% P97.5% Data distribution form In order to enhance the geochemical signature of
gold and its path®nders the contour level correspond-
Au 26 175 550 Unimodal-high values trend
As1 65 110 180 Unimodal ing to the 84% percentile …b 1 s† of the lognormal
As2 800 1950 4800 Unimodal-high values trend data populations was added to the contour maps
Bi 0.9 4.4 20 Unimodal-low values trend (Fig. 4).
Sb 52 158 470 Unimodal-low values trend Comparing Figs. 3 and 4 we observe that the use of
Te 38 75 148 Unimodal-low values trend
this new threshold on isoconcentration mapping led to
Se 5 32 110 Unimodal-low values trend
a better expression of gold, arsenic and bismuth halos,
whilst antimony, tellurium and selenium still do not
Bi (Fig. 2), Se, Sb and Te, thresholds were calculated de®ne clearly the gold anomaly.
at the 97.5% percentile …b 1 2s† of the probability
plot. In the case of gold, having a unimodal-high 4.3. Multielement halos technique
values trend distribution and showing a break point
at approximately the 5% level, threshold was calcu- Beus and Grigorian (1977) have shown that
lated at the intersection of the 97.5% percentile with geochemical halos around ore bodies can be de®ned
the straight-line AB (Fig. 2). In the arsenic bimodal better by the combination of two or more path®nder
case, the data population was partitioned into two elements. Multielement halos are less in¯uenced
sub-populations, As1 and As2 (Lepeltier, 1969) by the effects of random errors and consequently
and thresholds were calculated for each one of exhibit a closer relationship to structural geological
these sub-populations (As1, As2), according to the features associated with a mineralisation Thereby,
criteria that were applied to the unimodal popula- the reliability on the interpretation of the halos is
tions. The partition of the arsenic population has increased.
revealed the existence of a simple unimodal data Multielement halos (additive halos) are de®ned
population and a unimodal-high values trend data by the simple addition of path®nder element concen-
population. Table 2 presents the statistical para- trations normalised against their background values,
meters determined from Au, As, Bi, Sb, Te and Se or
probability plots. HX1Y ˆ …X1 =X0 1 Y1 =Y0 †; ¼; …XN =X0 1 YN =Y0 †;
For the contour maps the gridding method selected
was the triangulation with linear interpolation. This where X1, X2,¼, XN are concentrations of X in
method was chosen since it works best when data samples 1, 2,¼, N, Y1, Y2,¼, YN are concentrations
points are evenly distributed over the grid area and of Y in samples 1, 2,¼, N and X0, Y0 are background
is very effective at preserving break lines. values for X and Y data populations.
Fig. 3 presents the halos for gold and its path®nders The background values used for normalisation are
in the soil above the Marrancos mineralisation. These those presented in Table 2 (As-65 ppm; Au-26 ppb;
halos show that the geochemical anomalies based on Bi-0.9 ppm; Sb-52 ppb; Te-38 ppb; Se-5 ppb).
the 97.5% …b 1 2s† percentile contours (Lepeltier, According to Beus and Grigorian (1977), it is

Table 3
Statistical parameters calculated for the new data populations (lognormal distributions)

Elements P50% P84% P97.5% Data distribution form

As 1 Bi 2 7 13 Unimodal-high values trend

Sb 1 Se 1 Te 3 9 25 Unimodal-low values trend
As 1 Bi 1 Sb 1 Se 1 Te 8 25 112 Unimodal
6 A.P. Reis et al. / Journal of Geochemical Exploration 73 (2001) 1±10

Fig. 3. Geochemical halos for gold and path®nder elements, using the 97.5% percentile …b 1 2s† as threshold. Threshold values used as
departure for the contouring curves are of 550 ppb for Au, 4800 ppm for As, 22 ppm for Bi, 470 ppb for Sb, 145 ppb for Te and 110 ppb for Se.
 A.P. Reis et al. / Journal of Geochemical Exploration 73 (2001) 1±10 7

Fig. 4. Geochemical halos for gold and path®nder elements, using the 84% percentile (b 1 s) as threshold. Threshold values that were used as
departure for the contouring curves are of 175 ppb for Au, 1950 ppm for As, 4 ppm for Bi, 158 ppb for Sb, 75 ppb for Te and 32 ppb for Se.
8 A.P. Reis et al. / Journal of Geochemical Exploration 73 (2001) 1±10

Fig. 5. Geochemical halo for gold and additive halos for path®nder elements. Threshold values that were used as departure for the contouring
curves are of 175 ppb for Au, 7 for As 1 Bi, 9 for Sb 1 Se 1 Te and 25 for As 1 Bi 1 Sb 1 Se 1 Te (due to data normalisation, the additive
halos values have no dimension).

necessary to de®ne the threshold of the new data

population, which has been estimated at the 84% Table 4
percentile of its probability plot, i.e. using the same Geochemical halo dimensions for Au and combined path®nder
criterion as for monoelement populations. Table 3 elements
presents the statistical parameters determined from
Anomalous halos Maximum Maximum
As 1 Bi; Sb 1 Se 1 Te and As 1 Bi 1 Sb 1 Se 1 length (m) width (m)
Te probability plots.
Fig. 5 shows additive halos for gold path®nders in Au 590 230
As 1 Bi 650 370
the Marrancos mineralisation. Table 4 presents the
Sb 1 Se 1 Te 540 280
maximum values of length and width obtained for As 1 Bi 1 Sb 1 Se 1 Te 590 310
gold and for the new anomalous halos.
 A.P. Reis et al. / Journal of Geochemical Exploration 73 (2001) 1±10
Fig. 5 and Table 4 show that the additive halos
are wider and have similar lengths to gold anoma-
lous halo, with the exception of As 1 Bi. The asso-
ciation of As and Bi clearly enhance the size of
the geochemical signature. Furthermore, path®nder
elements like Sb, Se and Te that were ineffective
in outlining the gold anomaly are effective when
combined.
5. Conclusions
Using Au, As, Bi, Sb, Te and Se concentrations in
Marrancos soil samples, different methods were
applied in order to improve the representation of the
super®cial geochemical signature produced by the
mineral deposit.
The results lead to the following conclusions:
The use of the 97.5% percentile estimated in the
log-probability plot as anomaly threshold for the
data populations resulted in anomalies which may
be dif®cult to recognise.
The multielement halos technique transforms
ineffective path®nder elements such as Sb, Se and
Te into an effective composite path®nder of
the Marrancos mineralisation. This geochemical
mapping technique seems to be more ef®cient in
weak geochemical anomalies.
Arsenic and bismuth monoelement and multi-
element halos de®ne clearly the geochemical
anomaly of Marrancos gold deposit, which con®rm
their character as path®nder elements.
Acknowledgements
The authors would like to express their thanks to
the IGM of Portugal for supporting this project, to the
LaboratoÂrio Central de AnaÂlises of Aveiro University
for the gold analysis, to the Geosciences Department
of Aveiro University and to Programa Praxis XXI for
the scholarship granted to the ®rst author.
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