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Further study on deep penetrating geochemistry over the Spence porphyry

copper deposit, Chile

Article  in  Geoscience Frontiers · July 2011

DOI: 10.1016/j.gsf.2011.05.017

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 GEOSCIENCE FRONTIERS 2(3) (2011) 303e311

available at www.sciencedirect.com

China University of Geosciences (Beijing)

GEOSCIENCE FRONTIERS
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ORIGINAL ARTICLE

Further study on deep penetrating geochemistry over

the Spence porphyry copper deposit, Chile
Xuejing Xie*, Yinxiu Lu, Wensheng Yao, Jinfeng Bai

Institute of Geophysical and Geochemical Exploration, Chinese Academy of Geological Sciences, 84 Jinguang Road, Langfang,
Hebei 065000, China

Received 26 December 2010; accepted 11 May 2011

Available online 24 June 2011

KEYWORDS Abstract A study of deep penetrating geochemistrydthe surface exploration techniques for finding
Deep penetrating concealed mineral depositsdwas carried out over the Spence porphyry copper deposit in Chile by
geochemistry; Australian, Canadian and Chinese laboratories using selective weak leach methods and is briefly reviewed
Selective leach; here. Erratic and weak copper anomalies were obtained above the Spence deposit, which is concealed
Oxides; below a thick piedmont gravel cover. In the literature, such patterns are common in most of the weak
Sulfides; selective leach studies carried out over known buried deposits. During exploration in unknown area, such
Spence Cu deposit; weak leach techniques lead to some success and many dry holes. In this paper, stronger selective leaching
Chile methods are developed for oxides and sulfides, which may be the stable end products transformed and
accumulated by a mobile precursor phase carried upward through the overburden by gas or water through
long spans of geological time. The data obtained by the methods developed in this paper produced more
significant and consistent anomalous data than previous efforts. Consequently, the leach approaches
described here may increase the effectiveness of deep penetrating geochemistry in exploration for con-
cealed ore deposits.
ª 2011, China University of Geosciences (Beijing) and Peking University. Production and hosting by
Elsevier B.V. All rights reserved.

* Corresponding author.
E-mail address: xuejing_xie@126.com (X. Xie).
1674-9871 ª 2011, China University of Geosciences (Beijing) and Peking
University. Production and hosting by Elsevier B.V. All rights reserved.
Peer-review under responsibility of China University of Geosciences
(Beijing).
doi:10.1016/j.gsf.2011.05.017
Production and hosting by Elsevier
1. Introduction
Traditional exploration geochemistry has focused its effort on
studying the various types of secondary elemental dispersion
halos and trains, and primary dispersion halos exposed at the
land surface. It has obtained many successes in discovering ore
bodies hidden beneath thick layers of residual overburdens. But
it is much less efficient in discovering ore bodies concealed
deeply beneath various kinds of transported overburdens. So,
increasing attention is being focused on the development of deep
penetrating geochemistry, i.e. surface exploration techniques for
finding concealed mineral deposits. Numerous published case
studies, have documented super-composed geochemical
304 X. Xie et al. / Geoscience Frontiers 2(3) (2011) 303e311

covered by 50e100 m of piedmont gravels. So it is

impossible to use traditional surface geochemical exploration
methods to detect deposit concealed beneath such a thick
exogenic cover. Ten methods of selective extraction by labora-
tories from Australia, Canada and China were used to analyze
copper in soil samples in the deposit’s overburden. The results
were presented in a report written by Cameron (Cameron and
Xie, 2002). In present paper, the earlier works and problems
encountered are briefly reviewed, and new analytical approaches
are discussed in order to obtain better results.

2. Brief review of former works

Figure 1 Location of study area, outline map of the basement
geology of the Spence deposit, and soil sampling sites along an
eastewest traverse (taken from Cameron et al., 2004).
anomalies in transported overburden above buried mineral
deposits in many different environments. A variety of
approaches, including selective leaching of soils to extract the
mobile component of elements, has been applied in these studies
(Cameron, 1998; Mann et al., 1998; Wang, 1998; Kelley et al.,
2003).
In 1997, the project Deep-Penetrating Geochemistry, with
E. Cameron as project leader and sponsored by the Canadian
Mining Industry Research Organization (CAMIRO), was initi-
ated with the objective of providing the mining industry with
information relating to processes that may form surface anom-
alies over concealed deposits and providing comparative data on
methods used to detect these anomalies (Cameron, 1998). As
part of the CAMIRO Deep-Penetrating Geochemistry project,
sixty one soil samples were collected on a traverse that crosses
the buried Spence porphyry deposit, northern Chile (Fig. 1). The
soil samples were sieved and 80 mesh fraction samples were
sent to laboratories for analysis. On this traverse, the deposit is
In the Cameron and Xie (2002) report, it was concluded that the
Australia MMI-A leach, the Canadian ammonium acetate leach,
and the Chinese ammonium citrate leach give the better results of
the ten methods studied (Table 1; Figs. 2a, 3a and 4a). It is
postulated that the anomalies have been created by seismic
pumping of mineralized groundwater to the surface, and incor-
porated into secondary carbonate minerals in the soil. The
analytical methods that give the distinct contrast of Cu anomaly to
background are those that dissolve carbonate without dissolving
other minerals that may contain Cu derived from primary mineral
phases in the gravel.
The weaker leaching methodsdCanadian deionized water and
Enzyme leachdalso give good results, but are different in that
they dissolve little of the secondary minerals. Instead, they bring
into solution the mobile precursor phase of elements from
a deposit, before being incorporated into secondary minerals such
as carbonates.
3. Further discussion of the previous results
Twenty soil samples were collected along an east-west traverse
directly over the Spence Cu deposit with a horizontal sampling
interval of approximately 25 m (Figs. 2a, 3a and 4a); an
additional 41 samples were collected at 50 m intervals on both
sides of the known ore body. This pattern of different sampling
would obviously not be possible in routine geochemical
exploration of unknown ore bodies. More erratic and less
definitive patterns would be produced using only the uniform

Table 1 Comparison of the results of 10 selective extraction methods (3 median as threshold).

Method Median (ppb) 90th (ppb) Percentile 90th Percentile No. of samples
Median over deposit >3  Median
Deionized watera 321 500 1.6 0
NH4-citrate 2800 11,600 4.1 7
Na pyrophosphate 700 3200 4.6 5
Hydroxylamine HCl 1200 2100 1.8 2
Deionized waterb 27 101 3.7 5
Enzyme leach 66 201 3.1 6
MMI 545 3270 6.0 9
Ammonium acetate 1060 6240 5.9 10
Hydroxylamine 2250 8250 3.7 7
Aqua regia 35,730 54,210 1.5 0
a
Chinese method.
b
Canadian method.
 X. Xie et al. / Geoscience Frontiers 2(3) (2011) 303e311 305

Figure 2 a Plot of Cu determined by MMI-A in soils across the Spence Cu deposit along sampling traverse 7480500 N from west to east. The x
axis is in meters. The position of the ore body is identified by the horizontal shaded bar. The gap in the plot east of the deposit is land occupied by
the highway and an aqueduct. b Plot of Cu determined by MMI-A in soils across the Spence Cu deposit sampling traverse 7480500 N with
uniform sample spacing of 50 m.

50 m sampling layout (e.g. Figs. 2b, 3b and 4b). Similar
patterns such as these are common in most of the published
results of selective leach studies over known buried deposits.
Such weak extraction techniques will miss promising targets
and delineate false anomalies, especially in regional explora-
tion with wide-spaced sampling for delineation of promising
target areas. During exploration in unknown regions such
methods lead to some success, but also lead to many dry holes
(Cameron et al., 2004).
Cohen et al. (2010), citing studies of Seneshen (1997), Gray
et al. (1999) and Rutherford (2002), conclude that one feature
common to selective extraction data is the high degree of
spatial variability over small meter-scale distances. They
conclude that such variations over short distances
(meter-scale) simply reflect the distribution of the migration
paths (fractures and other discontinuities in the regolith)
within which elements may concentrate. Such pathways
produce discrete anomalies within surface transported regolith
until subsequent processes laterally redistribute those trans-
ported elements. Dalrymple (2007) considered that such vari-
ation is the result of unjustified leaching reaction conditions,
e.g., temperature, pH, extraction time, colloid formation and
precipitation. From a study of the selective extraction
geochemistry for copper exploration in northern Chile, Kelley
et al. (2003) concluded that the selection of the most appro-
priate method should be based on the deposit type being
sought, the nature of the overburden, and the stability of the
leach method for this overburden. In the arid environment of
306 X. Xie et al. / Geoscience Frontiers 2(3) (2011) 303e311

Figure 3 a Plot of Cu determined by ammonium acetate pH 5 in soils across the Spence Cu deposit sampling traverse 7480500 N from west to
east. The x axis is in meters. The position of the ore body is identified by the horizontal shaded bar. The gap in the plot east of the deposit is land
occupied by the highway and an aqueduct. b Plot of Cu determined by ammonium acetate pH 5 in soils across the Spence Cu deposit sampling
traverse 7480500 N with a uniform sample spacing of 50 m.

northern Chile, dispersion of metals from buried deposits
through transported covers are in mobile forms such as
ions, micro-particles carried up by water or gas through
electrochemical processes (Hamilton, 1998), or by cyclical
dilatancy pumping, i.e. the structurally induced permeability
cycling that occurs before and after earthquakes (Cameron and
Xie, 2002). According to these models, the mobile forms of
elements dispersed through the overburden are unstable. It is
postulated that they will change during the long span of
geological time to their end products of various, more stable
and complex oxide forms. A stronger selective leach is needed
to leach out various forms of oxide, so that more
homogenous and significant anomalous patterns can be
obtained.
4. The new micro-phase methods
So-called “phase analysis” methods to determine various phases
(e.g. oxide, sulfides, etc.) in ore samples were originally developed
in Russia. In China, these methods have been further developed
for the determination of various phases of metals in geochemical
anomalous soil samples with the aim of evaluating the significance
of metal anomalies (Gong, 1994, 2007). In this paper, phase
analysis methods have been modified and further developed to
determine the oxidized and sulfide phases of Cu in soil samples
collected in exogenic overburden. Because the concentration of
elements in these phases is in the ppm and sub-ppm range, the
analytical methods described below are more appropriately
referred to as micro-phase analysis.
 X. Xie et al. / Geoscience Frontiers 2(3) (2011) 303e311 307

Figure 4 a Plot of Cu determined by the Chinese method NH4-citrate for adsorbed elements in soils across the Spence Cu deposit sampling
traverse 7480500 N from west to east. The x axis is in meters. The position of the ore body is indicated by the horizontal shaded bar. The gap in the
plot east of the deposit is land occupied by the highway and an aqueduct. b Plot of Cu pattern determined by NH4-citrate leach across the Spence
Cu deposit sampling traverse 7480500 N with a uniform sampling interval of 50 m.

4.1. Experimental
The determination methods for the oxidized phase and primary
sulfide phase were developed (Bai and Lu, in press) and its
analytical procedures are described below. Two types of soil
samples, 80 mesh fraction samples and the 120 mesh size
processed samples, were determined by these methods in order to
investigate if the finer grained samples would lead to consistent
anomalous results.
4.1.1. Determination of the oxidized phase of Cu in 80 mesh
samples
Weigh 0.5e1 g of soil sample; add 50 mL dilute H2SO4 (1:9) and
0.5e1.0 g Na2SO3; shake in an agitator for 1 h; filter by suction
through 2 mm fiber; add 2 mL HF to the filtrate; heat until nearly
dried. Add 5% HCl to dissolve the residue and determine Cu by AAS.
4.1.2. Determination of the primary sulfide phase of Cu in 80
mesh samples
Add 40 mL bromine-menthol (5:95) to the residue on the fiber
filter; shake in an agitator for 1 h; add 2 mL HF; evaporate to
dryness. Add HCl (5%) to dissolve the residue and determine Cu
by AAS.
4.1.3. Determination of the oxidized phase of Cu in processed
samples
80 mesh samples are pulverized to pass 120 mesh in a small
agate high aluminum ball mill. Weigh 0.5e1 g of processed
sample and determine the oxidized phase Cu using the above
procedure for determination of the oxidized phase of Cu.
4.1.4. Determination of the primary sulfide phase of Cu in
processed samples
The procedure is the same as for determination of the primary
sulfide Cu in 80 mesh samples.
Data obtained are listed in Tables 2 and 3. The central columns
framed by bold lines are data directly over the Spence deposit.
From these two tables, it is clear that there are very consistent
contrasts between anomalous values over concealed deposit and
values over adjacent barren areas.
308 X. Xie et al. / Geoscience Frontiers 2(3) (2011) 303e311

Table 2 Cu data of oxidized phase along line 7480500 N.

Nos. Cu oxidized phase (ppm) Nos. Cu oxidized phase (ppm) Nos. Cu oxidized phase (ppm)
80 mesh Processed 80 mesh Processed 80 mesh Processed
473549 15.8 18.2 474473 16.7 20.8 475071 16.8 16.8
473595 16.8 17.2 474521 22.8 22.8 475120 12.7 14.6
473650 18.8 16.7 474557 25 25 475279 18.3 18.3
473693 16.7 15 474586 22.7 22.7 475316 15.8 16.7
473745 18.7 16.5 474615 25 25 475367 17.2 16.7
473792 16.7 16.5 474640 21.7 21.7 475412 16.7 16.5
473840 16.7 16.5 474665 16.7 19.9 475463 15.8 15.8
473890 18.4 16.7 474698 25 25 475511 16.7 16.8
473940 15.8 15 474723 29.2 29.2 475564 16.7 17.6
473989 16.8 17.2 474746 21.8 21.8 475611 12.5 16.5
474039 16.7 16 474771 26.7 26.7 475659 14.8 16.2
474087 15.8 16.7 474791 29.5 29.5 475709 15 15
474134 16.7 16.7 474810 29.5 29.5 475758 16.7 16.7
474184 16.7 17.2 474826 26.7 26.7 475808 15.8 15.8
474233 15.8 16.7 474855 29.2 29.2 475857 20 20
474286 17 16.7 474876 26.7 26.7 475907 15 15
474319 16.2 16.2 474911 26.7 26.7 475951 15 15
474380 15.8 16.7 474937 29.2 29.2 476004 16.7 16.5
474425 16.7 17 474958 29.2 29.2 476049 20.8 20.8
474975 22.7 25 476097 21.7 21.7
475002 25 15.8 Average 19.55 19.64
475030 15.8 15.8
Note: Shaded numbers are sample above the ore body and shaded data are anomalous values.

Table 3 Cu data of Sulfide phase along line 7480500 N.

Nos. Cu sulfide phase (ppm) Nos. Cu sulfide phase (ppm) Nos. Cu sulfide phase (ppm)
80 mesh Processed 80 mesh Processed 80 mesh Processed
473549 7.1 10.5 474473 21.4 14.7 475071 14.7 14.2
473595 11.2 20.8 474521 14.6 25 475120 21.4 17.9
473650 7.1 14.2 474557 21.4 21.4 475279 10.7 10.7
473693 8.4 15 474586 14.6 20.8 475316 10.7 14.2
473745 7.1 14.2 474615 21.4 34 475367 17.9 17.9
473792 15.4 14.5 474640 14.7 24 475412 17.9 16.7
473840 15.9 15.2 474665 25 39.3 475463 17.9 17.1
473890 14.2 15 474698 14.3 24.7 475511 14.2 17.5
473940 7.1 14.6 474723 32.1 28.2 475564 14.2 14.2
473989 13.9 16.2 474746 14.7 22 475611 10.7 10
474039 14.2 14.2 474771 21.4 29.9 475659 17.9 13
474087 14.4 14.4 474791 12.7 25 475709 21.4 21.4
474134 10.7 14.2 474810 30.8 21.5 475758 17.9 21.4
474184 8.6 17.9 474826 39.3 21.4 475808 17.9 21.4
474233 14.6 17.9 474855 21.4 21.4 475857 14.2 21
474286 10.7 10.7 474876 13.7 23.5 475907 14.2 17.9
474319 21.4 10.7 474911 17.9 21.4 475951 17.9 14.2
474380 10.7 21.4 474937 64.3 65 476004 14.2 32.1
474425 14.2 21.4 474958 17.9 25 476049 44.3 20.8
474975 14.9 18.7 476097 15 15
475002 32.1 16.7 Average 17.47 19.78
475030 12.9 21.4
Note: Shaded numbers are sample above the ore body and Shaded data are anomalous values.
 X. Xie et al. / Geoscience Frontiers 2(3) (2011) 303e311 309

Figure 5 a Plot of Cu in oxide micro-phase ( 80 mesh samples) with a uniform sampling interval of 50 m. Position of concealed ore body is
indicated by the shaded horizontal bar. b Plot of Cu in oxide micro-phase (processed samples) with uniform sampling interval of 50 m. Position of
concealed ore body identified by horizontal shaded bar.

5. Discussion explain the strikingly better result obtained from processed

Fig. 5a shows the variation of oxidized phase of Cu over the
Spence deposit with a uniform sampling layout (50 m interval).
Fig. 5b shows the variation of oxidized phase of Cu in the pro-
cessed samples. There is little difference between determinations
of the oxidized phase of copper, whether the sample is processed
or not.
Fig. 6a and b show the variation of the primary sulfide phase of
Cu in 80 mesh samples and in processed samples, respectively.
It is evident that the anomaly patterns of the sulfide phase of Cu
derived from processed samples is more homogenous and
significant than that derived from the original 80 mesh samples
(Table 4).
The Cu sulfide phase may originally penetrate through the
exogenic gravel to reach the surface in various complex forms of
SO24 dissolved in saline water (Cameron et al., 2010). Alterna-
tively, the primary Cu sulfide in ore may be in nanoscale and
adhered on micro-bubbles of gas or water vapor as it migrates
upwards to the surface (Xie and Wang, 2003). This could help
samples for Cu sulfide determination. After pulverizing to 120
mesh, part of the suspected nanoscale primary Cu sulfide phase
incorporated into more resistant secondary minerals will be
exposed and taken into solution. Further study is required to
verify this assumption.
6. Concluding remarks
1. Micro-phase analytical methods for copper that are
developed in this paper can be used in geochemical
exploration, or incorporated with selective leach tech-
niques in detailed efforts to increase the success rate for
finding porphyry copper deposits concealed beneath desert
terrains.
2. The existence of micro-phases of sulfide ore-minerals in
exogenic covers can serve as more concrete evidence for the
existence of buried ore deposits.
3. Further studies are needed to apply this method to other metal
deposit exploration and in other cover terrains.
310 X. Xie et al. / Geoscience Frontiers 2(3) (2011) 303e311

Figure 6 a Plot of Cu in sulfide micro-phase ( 80 mesh samples). Position of concealed ore body identified by horizontal shaded bar. b Plot of
Cu in sulfide micro-phase (processed samples) with uniform sampling interval of 50 m. Position of concealed ore body identified by horizontal
shaded bar.

Acknowledgments

The authors wish to thank Prof. Gregory A. Davis for his

Table 4 Comparison of different methods of micro-phase Cu
suggestion and comments to improve the scientific presentation of
analysis.
this paper. Thanks are also given to the Ministry of Land and
Method Median No. anomalous Resources and the Ministry of Science and Technology for the
(ppm) samples, 20 ppm research funding of the projects: SinoProbe 04, 973 Project
as threshold 2007CB411406 and 863 Project 2007AA06Z133.
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