13.

24 Exploration Geochemistry
DR Cohen, University of New South Wales, Sydney, NSW, Australia
RJ Bowell, SRK Consulting, Cardiff, UK
ã 2014 Elsevier Ltd. All rights reserved.

13.24.1 Introduction 623

13.24.1.1 Role of Geochemistry in Mineral Exploration 623
13.24.1.2 Geochemical Processes and Terrains 623
13.24.2 The Primary Environment 624
13.24.3 The Secondary Environment 627
13.24.3.1 Weathering and Dispersion 627
13.24.3.2 Arid and Deeply Weathered Terrains 629
13.24.3.3 Transported Cover 630
13.24.3.4 Glaciated Terrains 633
13.24.3.5 Other Example Techniques 635
13.24.3.5.1 Heavy indicator minerals 635
13.24.3.5.2 Hydrogeochemistry 635
13.24.3.5.3 Biogeochemistry 638
13.24.3.5.4 Vapor and gas geochemistry 638
13.24.4 Regional Geochemical Mapping 639
13.24.5 Analysis 641
13.24.6 Geochemical Data Interpretation 644
Acknowledgments 646
References 646

13.24.1 Introduction These may include relative enrichment or depletion of ele-

13.24.1.1 Role of Geochemistry in Mineral Exploration
Geochemical prospecting for mineral deposits is an ancient
technique. For millennia, prospectors have sought Fe and Cu
stains on rocks, which result from the oxidation of sulfide
mineral deposits and the subsequent dispersion of the prod-
ucts, as possible indicators of mineralization (Rose et al.,
1979). Panning for Au and other heavy minerals is also an
ancient and successful geochemical prospecting method
(Boyle, 1979).
Modern methods of geochemical exploration came into
practice in the 1930s in Russia and Scandinavia, and post-
WW II in North America. This was facilitated by the ongoing
development of rapid and accurate analytical techniques capa-
ble of detecting elements at concentrations below the levels
that generate visible anomalies. Continued developments have
provided the routine availability of sensitive, multielement
analytical methods that allow the detection of subtle effects
of mineralization on the surrounding environment. Geochem-
istry is a major contributor to mineral exploration programs
from regional reconnaissance to deposit scales.
Geochemical exploration techniques must take into ac-
count the style of mineralization and its geological setting,
the evolution and characteristics of the weathered zone (rego-
lith), and the general physical, chemical, and biological char-
acteristics of the environment in which exploration is
undertaken – the ‘geochemical landscape’ (Fersman, 1934;
Fortescue, 1992; Perel’man, 1955). Most applications of geo-
chemistry in mineral exploration focus on detecting and map-
ping patterns in the chemical composition of the lithosphere
or biosphere that can be linked to the effects of mineralization.
ments, or changes to element speciation or mineralogical
associations.
In designing geochemical exploration surveys, various com-
binations of sampling media, sample processing, geochemical
analysis methods, and data processing and interpretation
models can be selected from a wide array of options. In many
cases, such selections need to be tested by way of orientation
studies around well-characterized mineralized targets. Regional
geochemical surveys in particular can employ a variety of sam-
pling media (from the more conventional rocks, soils, glacial
materials, stream sediments, and waters to the less conventional
biota and soil gas) and analytical components (from elements,
species, and minerals to isotopes).
13.24.1.2 Geochemical Processes and Terrains
Geochemical processes that affect the form and distribution of
elements may be broadly separated into the environment
(deep-seated or surficial) and the stage of dispersion (primary
or secondary) under the classification system of Rose et al.
(1979). In general, primary geochemical dispersion occurs in
deep environments and secondary dispersion in surface envi-
ronments, although some mineral deposits (e.g., supergene Au
or Cu) form in the surficial environment. Dispersion results in
the development of geochemical haloes – and exploration
targets – that are almost invariably larger than the mineralized
body itself. Element associations or concentration zonation
may also create vectors toward mineralization.
Primary dispersion mainly involves the migration of ele-
ments of economic interest due to processes, such as the
formation and crystallization of magmas or hydrothermal

Treatise on Geochemistry 2nd Edition http://dx.doi.org/10.1016/B978-0-08-095975-7.01127-X 623

624 Exploration Geochemistry
activity. Locally, these processes can lead to enrichment or
depletion of elements generating geochemical anomalies. The
redistribution of chemical elements at, or near, Earth’s surface
due to weathering, transportation, sedimentation, and/or bio-
logical activity, is classified as secondary dispersion. Mapping
the effects of such processes is used to detect concealed or
buried mineralization (Cameron et al., 2004).
Analysis of the characteristics of different terrains forms the
basis for the development of conceptual geochemical models
and subsequent design of exploration programs. Conceptual
models have been developed for a number of geochemical
landscapes and environments, including those displaying an-
cient and/or modern deep weathering and duricrust formation
(Anand and Butt, 2010; Butt et al., 2005) or the effects of recent
glaciation (Kauranne et al., 1992; McClenaghan et al., 2001).
13.24.2 The Primary Environment
Most geochemical exploration studies in the primary environ-
ment may be classified as lithogeochemistry (Govett, 1983).
The purpose of many lithogeochemical surveys has been the
identification of element enrichment or depletion in zones
surrounding mineralized rocks. Alteration of wall rock com-
monly provides the most discriminating evidence of geochem-
ical changes (Boyle and Jonasson, 1973; Large et al., 2001) and
is commonly reflected in mineralogical changes as described
for many of the mineral deposits elsewhere in this volume.
Such an approach can be used to define semiregional- to
regional-scale lithogeochemical patterns, such as the chalco-
phile corridors (Smith et al., 1989) observed in regions such as
the Otago Schist Belt in New Zealand (Craw et al., 2007).
The formation of most ore deposit types is the result of
atypical geochemical processes that affect the rock package
surrounding, or adjacent to, the actual mineralized zone. Iden-
tifying terrains in which such processes have operated assists in
the selection of areas for detailed exploration. Lithogeochem-
istry in mineral exploration has, therefore, evolved over the last
decade from studies that largely focus on deposit-scale geo-
chemical patterns around mineralized systems (Govett, 1983)
to the identification of fertile provinces for mineral deposits,
especially in the early stages of exploration, by measuring
regional geochemical features that reflect processes that can
lead to the formation of ore deposits (Cohen et al., 2010). In
many exploration programs, this is contemporaneous with
regional or prospect level mapping.
Apart from whole-rock geochemistry and mineralogy, litho-
geochemical studies in exploration may include trace element
patterns in specific minerals such as pyrite or in fluid inclu-
sions (e.g., Buchanan, 1981) and stable isotope ratios.
Example: Lithogeochemical discrimination of barren versus
fertile intrusions.
Porphyry Cu deposits can develop from melts that have
been subject to repeated cycles of replenishment by primitive
magma and partial crystallization (Rohrlach and Loucks,
2005). With each cycle, incompatible components and vola-
tiles become progressively enriched in the residual melt, result-
ing in conditions that are optimal for Cu mineralization.
Increased water content suppresses plagioclase crystallization
relative to hornblende, resulting in geochemical effects such as
an increase in the ratio of Sr (plagioclase-hosted) to Y
(hornblende-hosted) (Richards, 2011). Systematic whole-
rock analysis of igneous rocks can potentially discriminate
fertile hydrous magmatic events, presenting a way of screening
extensive packages of volcanic rocks in regional assessment of
porphyry Cu prospectivity in volcanic arc terranes. Based on an
extensive whole-rock reference suite of samples from volcanic
arcs in the northwest Pacific that are fresh or display weak
propylitic alteration, Sr/Y has been plotted against SiO2 for
‘barren’ and ‘productive’ terranes (Figure 1). Although there
is some overlap between the suites, the productive suite tends
to have relatively elevated Sr/Y over a wide range of rock
compositions.
Example: Lithogeochemical assessment of alteration patterns.
Lithogeochemical vectors to orebodies may be obscured by
primary lithological variation and alteration not directly re-
lated to mineralization. Pearce element ratio (PER) analysis
of major components can be used to identify and eliminate
nonhydrothermal sources of variation, delivering better dis-
crimination of mass transfers related to hydrothermal alter-
ation alone (Madeisky and Stanley, 1993; McQueen and
Whitbread, 2011).
Mafic and felsic lithologies in the cluster of porphyry
Cu–Mo and epithermal Cu–Ag
Au deposits of the Collahuasi
district in Chile have been modeled by Urqueta et al. (2009).
The objective was to determine background variability and
discriminate between fresh or propylitically altered units and
those with a hydrolytic alteration overprint. A PER diagram for
alkali elements versus Al allows discrimination between
feldspar-rich units that are (1) unaltered and plot along the
feldspar control line, (2) have been sericitized and plot toward
the muscovite control line, and (3) have been argillically
SiO2 (wt %)
45 50 55 60 65 70 75
100
70
50
30
Sr
Y
20
10
General limits for an unmineralized reference
suite from <6 Ma volcanic arc samples
7
5
Figure 1 Discriminant plot of Sr/Y versus SiO2 showing samples from a
suite of samples associated with Cu–Au ore deposits (♦) compared with
an extensive barren reference rock suite (shaded area) from volcanic arcs
in the northwest Pacific. Modified from Rohrlach BD and Loucks RR
(2005) Multi-million-year cyclic ramp-up of volatiles in a lower crustal
magma reservoir trapped below the Tampakan copper–gold deposit by
Mio-Pliocene crustal compression in the southern Philippines. In: Porter
TM (ed.) Super Porphyry Copper and Gold Deposits: A Global
Perspective. Adelaide: PGC Publishing.

altered and plot toward the kaolinite and chlorite control line
(Figure 2). An alteration index derived from such PER dia-
grams has been used to quantify the degree of metasomatic
exchange during hydrolytic alteration and permits areas of the
most intense hydrothermal alteration at a district scale to be
mapped (Figure 3).
Example: Zircons and the TerraChron method.
Zircons have long been used as a geochronometer, but their
process-sensitive trace element composition also provides use-
ful information for understanding crustal development
(Harley and Kelly, 2007). Because they are physically and
chemically stable over long periods of time, they are preserved
in regolith.
The TerraChron method integrates U–Pb dating, Hf isoto-
pic analysis, and trace element analysis of zircons obtained
from drainage samples to characterize their source rocks
(O’Reilly et al., 2004). The method can provide an overview
of the geological history of a region and its crustal evolution
and is ideally suited for regional work where the geology is
poorly known or for correlating terranes separated by later
tectonic events. Isolation of different populations of zircons,
based on size, color, and chemical composition, allows differ-
ent events to be characterized, including the age of formation,
the modeled ages of source rocks, the composition of parent
rock types, and their source region. The compilation of
this information for a large number of zircon populations is
presented on an ‘event signature diagram’ (Figure 4). When
preexisting crust is being reworked, the results follow the evo-
lutionary paths for the crust at a given age (toward the lower
left of the figure). If juvenile material is added, as might occur
Collahuasi porphyry
Ines porphyry
K-feldspar and plagioclase
control line (m = 1)
0.20
(2Ca + Na + K) / Zr
0.15
0.10
a
0.05
0.00
0.05 0.10 0.15
Figure 2 PER diagrams of selected elements against the conservative element Zr to describe the changes during hydrolytic alteration for felsic units,
Collahuasi district, Chile. Arrow (a) represents the trend from unaltered to sericitized lithologies and (b) the trend for alkali-bearing units altered to
kaolinite/pyrophyllite or chlorite group minerals, based on mineralogical control lines. Modified from Urqueta E, Kyser TK, Clark AH, Stanley CR, and
Oates CJ (2009) Lithogeochemistry of the Collahuasi porphyry Cu–Mo and epithermal Cu–Ag (–Au) cluster, northern Chile: Pearce element ratio vectors
to ore. Geochemistry: Exploration, Environment, Analysis 9: 9–17.
Exploration Geochemistry 625
during significant compressional or extensional events, the re-
sults trend to the upper left, normal to the evolutionary paths.
Hafnium isotopic and rock compositions deduced from trace
element data provide further insight into the tectonic events
that have occurred (e.g., rifting vs. subduction). The distribu-
tion of magmatic crystallization ages for the zircon popula-
tions versus the mean crustal residence age of the source for the
Mt. Isa Eastern Succession indicates repeated extension and
magmatism superimposed on an ancient crust. By contrast,
results for southern Norway indicate continental build up of
new crust at a continental margin with no indication of ancient
crust.
Example: Rutile trace element chemistry applied to exploration,
Big Bell Au deposit, Australia.
Rutile is a common accessory mineral that can provide a
potential lithogeochemical exploration guide. The abundance,
grain size, and chemical composition appear to reflect the
intensity of alteration and mineralization (Scott, 2005). Rutile
trace element geochemistry, particularly V, W, and Sb, has been
applied to distinguish the intensity of mineralization at
Hemlo Au deposit in Canada (Harris, 1989). It can be partic-
ularly useful where rutile is concentrated in regolith derived
from a mineralized protolith in which the endogenic com-
position of the precursor mineralization is retained in the
resistant rutile.
Mineralization at the Big Bell deposit occurs in a metamor-
phosed volcano-sedimentary sequence within the Murchison
Province, Western Australia (Scott and Radford, 2007). Gold
occurs as a disseminated component along with abundant
sulfides as 5–10 mm grains within pyrite. Weathering in the
Rosario porphyry Dacite 1
Rhyolite 1 Dacite 2
Muscovite
control line
(m = 0.33)
Kaolinite and
chlorite
control line
b
(m = 0)
0.20 0.25 0.30
Al / Zr
626 Exploration Geochemistry

Alteration
index (%)
5 km

79.4
73.7
68.0
63.7
59.4
55.1
50.8
46.5
42.2
38.6
35.7
32.8
30.0
28.3
26.7
25.0
22.7
20.3
18.0

>56
40–56
29–40
24–29
<24

Mineralized
zones and
structures

Figure 3 Map of the modified alteration index in the Collahuasi district, Chile. Mineralized centres are indicated in black. Modified from Urqueta E,
Kyser TK, Clark AH, Stanley CR, and Oates CJ (2009) Lithogeochemistry of the Collahuasi porphyry Cu–Mo and epithermal Cu–Ag (–Au) cluster,
northern Chile: Pearce element ratio vectors to ore. Geochemistry: Exploration, Environment, Analysis 9: 9–17.

area extends to 80 m depth with up to 5 m of alluvium cover.

200
f

cr of
t

Rutile has a characteristic V þ Fe þ W þ Sb geochemical signa-

Ga on o
Ga of
us

t
ol n

us

Ga tion
us

S. Norway
cr
(Age of magma – Hf model age of source)

cr
ti
Ev

ture in the Au-bearing zone and this signature extends 200 m

olu

2. volu
Mean crustal residence age of source

Ev
5

0 into the footwall (Figure 5). This feature provides a potentially

E
1.

0
2.

larger target for detecting proximity to Au mineralization than

-200 the dispersion of Au in the protolith or regolith.
Example: Fluid inclusion chemistry in exploration.
-400 Fluid chemistry of quartz from the Rössing mine in central
Namibia has been used to differentiate U-bearing and barren
-600
Ju leucogranite pegmatites (Nex et al., 2002). Uranium mineral-
ve
ni
le ization at the Rössing mine is primarily located in post-
Mixing collisional sheeted leucogranites. Uranium occurs as
-800
ing

uraninite and beta-uranophane in the economic SJ area of

rk
wo

the Rössing pit and as pyrochlore group minerals in the un-

Re

-1000 economic SH area. Manometric determination of the propor-

-1200
1000 1400
207
Pb/ 206Pb age (Ma) for magma generation
Figure 4 Example of an event signature diagram for detrital zircons
from the Mt. Isa region in Australia and southern Norway terranes.
Modified from O’Reilly SY, Griffin WL, and Belousova EA (2004)
TerraneChron – Delivering a competitive edge in exploration. Predictive
Mineral Discovery Under Cover. Symposium for the Society of Economic
Geologists, 27 September–1 October 2004, Perth.
Mount Isa
mineralization age tions of H2O, CO2, and noncondensable phases (mostly CH4)
in quartz fluid inclusions within the leucogranite displays
1800 2200 2600 discrete differences between the two styles of U-bearing leuco-
granites (Figure 6). Fluid geochemistry of sheeted leucogra-
nites from the SH area exhibits lower absolute water contents,
lower H2O/CO2 ratios, and low total fluids compared to those
from the SJ area. Fluid geochemistry and large ion lithophile
element data indicate that the occurrence of the SJ anomaly as
a major economic U orebody is linked to high water and total
fluid contents.
 Exploration Geochemistry 627

Slope = 2 Andes
Con
Shaft
Virginia
40 Shaft C and C
Shaft
0

-2
(Fe + V + Cr) x 103

30 -4 0

– +6
Slope = 1 -2
20
Altered andesite
+4
Granodiorite
Quartz vein
10 Big Bonanza +2
Zone
Ore Fault
+2
Altered
-2 Whole rock d 18O 200 m
Unaltered
0
0 10 20 30 Figure 7 Variations in whole-rock d18O in the vicinity of the contact
(W + Nb + Sb + Ta) x 103 between granodiorite and hydrothermally altered andesites, including the
Big Bonanza mineralized zone, Comstock, Nevada, USA. Modified from
Figure 5 Trivalent versus pentavalent and hexavalent ions in rutiles (on Criss RE, Singleton MJ, and Champion DE (2000) Three dimensional
an atomic basis) at the Big Bell Au deposit, Australia. Modified from Scott oxygen isotope imaging of convective fluid low around the ‘Big Bonanza’,
KM and Radford NW (2007) Rutile compositions at the Big Bell Au Comstock Lode mining district, Nevada. Economic Geology 95: 131–142.
deposit as a guide for exploration. Geochemistry: Exploration,
Environment, Analysis 7: 353–361. and is almost totally surrounded by rocks having much lower
d18O values (1.0 to 4.4%; Figure 7). On a regional scale, the
100 d18O values are also influenced by movement of hydrothermal
SJ area
fluids up other major faults in the area. Such geochemical
patterns allow targeting of mineral exploration at a semi-
SH area
regional scale.
The use of oxygen isotopes in lithogeochemical exploration
for volcanic-hosted massive sulfide (VMS) deposits is discussed
by Coriveau and Spry (Chapter 13.7).
H2O
10
CO2 13.24.3 The Secondary Environment
13.24.3.1 Weathering and Dispersion
Weathering is essentially the process by which minerals that are
normally stable within the crust break down near-surface
under the effects of water (hydrolysis and Hþ attack) and O2
(oxidation) to form supergene or secondary minerals, with the
1
loss of some more mobile elements (See Chapter 7.3). Feld-
1 10 100 spars typically weather to clays and silica, ferromagnesian min-
erals to secondary Fe oxides, and some Mg phases and sulfides
Total fluids (μmol g-1 of quartz)
to Fe oxides (depending on composition). The resulting mate-
Figure 6 Total fluid extraction versus H2O/CO2 in pegmatites from the rial is commonly referred to as regolith and includes everything
U-mineralized SH area and unmineralized SJ area, Rössing mine, from partially weathered rock to soils, sediments, and other
Namibia. Modified from Nex P, Herd D, and Kinnaird J (2002) Fluid materials that blanket Earth’s surface. Regolith is generally
extraction from quartz in sheeted leucogranites as a monitor to styles of
dominated by silicate minerals but in more arid regions may
uranium mineralization: An example from the Rössing area, Namibia.
be dominated by carbonates or secondary Fe oxides (Cameron
Geochemistry: Exploration, Environment, Analysis 2: 83–96.
et al., 2005). These components may host elements dispersing
Example: Variations in d18O resulting from hydrothermal from underlying mineralization (McQueen, 2008). Regolith
alteration around the Comstock Lode, Nevada. features are an integrated expression of geology, climate, land-
Whole-rock analyses of propylitized andesites display forms, geomorphic processes and landscape evolution, and
an intricate and conformable relationship between the ore- close generic relationships with landforms.
body and a deep gyre of elevated d18O meteoric-hydrothermal Various redox, acid–base, and hydrolysis processes in rego-
fluid that circulated along and above the Comstock fault, lith recycle both minerals and their associated elements, con-
near the contact of the Davidson granodiorite (Criss et al., tributing to the gradual dispersion of less mobile elements
2000; Singleton and Criss, 2002). The core of this gyre away from mineralization (Figure 8). For example, Cu released
(d18O ¼ 0–3.8%) encompasses the Big Bonanza mineralization from oxidizing sulfides under strongly acidic conditions will
628 Exploration Geochemistry

Increasing age of mineral phase in regolith

Less transitory metal contents
Acid–base and redox reaction Hydration–dehydration reaction
element recycling element recycling

Variable loss of highly

mobile elements
Adsorbed Mn oxides
Soluble & exch. Cryst. Resistate
Carbonates & Silicates
phases species Fe oxides minerals
am. Fe ox.
Organics

Progressive accumulation
of less mobile elements Progressive degradation of
Stabilization and fixation most primary minerals
of main regolith pattern Redistribution of elements

Figure 8 Redistribution and recycling of major and trace elements during regolith evolution.

Primary between these phases and goethite results in ‘reworking’ of

mineral trace elements and affects their dispersion patterns in relation
Initial to their original source.
weathering Elements can be assigned to three groups according to their
typical response to weathering. The first are elements bound in
Fe2+ resistate mineral phases, such as Ce in monazite and Zr in
Oxidation zircon, and whose mobility and geochemical dispersion de-
and/or
hydrolysis
pend on physical erosion processes that affect the landscape.
The second includes elements with a high degree of mobility,
Fe(OH)3 Strongly adsorbs such as B, Na, and Cl. The third are elements that are typically
other cations released from their primary phases during weathering and
Dehydration (e.g., Cu) which may themselves form secondary minerals or be retained
and high degree
of substitution
or absorbed by other secondary minerals, such as clays,
FeO.OH for Fe carbonates, and Fe–Mn oxyhydroxides in the regolith. Some
elements span more than one group, depending on their pri-
Rehydration Dehydration/ mary association (e.g., U in zircon as opposed to less stable
hydration U-bearing phases).
The secondary geochemical dispersion of elements can be
divided into three main components:
Fe2O3 Fe2O3
Maghemite Hematite 1. Clastic or physical dispersion involving the transportation
Conversion and deposition of solid particles under the effects of grav-
ity, wind, water, and ice. The transportation of mineral
material downstream by ice and wind and its redeposition
Weakly adsorbs other cations and are controlled by a range of mechanical processes, whereas
low degree of substitution for Fe
the general pattern is one of a progressive reduction in the
Figure 9 Evolution of Fe oxyhydroxides in the secondary environment. proportion of particles related to the mineralized body
being eroded as distance from the deposit increases; local
effects may have a strong influence on mineral and ele-
reprecipitate or adsorb onto the surface of minerals such as Fe ment abundances, especially heavy minerals, such as Au
oxyhydroxides if the pH values rise due to interaction of solu- (Cohen et al., 2005a,b).
tions with minerals such as carbonates. Iron is released as Fe2þ 2. Hydromorphic or chemical dispersion involving transpor-
from most primary minerals and undergoes oxidation fol- tation of elements as dissolved constituents or colloids. The
lowed by a series of dehydration steps from ferrihydrite to controls on dispersion largely revolve around the processes
hematite (Figure 9). Many of these secondary Fe minerals or conditions under which elements are mobilized or
have a strong affinity for chalcophile elements (Bowell, immobilized.
1994a). Whereas goethite has a high capacity to adsorb and 3. Biogenic dispersion by which materials are moved (chem-
incorporate other cations into its structure, hematite and ically and physically) by biological activity, such as
maghemite have a much lower capacity (Xie and Dunlop, termitaria development or the action of plants and micro-
1998). Conversion of hematite to maghemite and cycling organisms on soil components (Dunn, 2007).
 Exploration Geochemistry 629

13.24.3.2 Arid and Deeply Weathered Terrains essential for effective geochemical exploration program design
(Anand and de Broekert, 2005; Anand and Paine, 2002; Bamba
Arid and semiarid regions occupy approximately 30% of
et al., 2002; Butt et al., 2000; McQueen, 2008). New regolith
Earth’s exposed landmass (Levinson, 1980). In these regions,
models have affected the interpretation of geochemical disper-
the products of weathering (regolith) form a mantle that
sion data and anomalies.
ranges in depth from a few millimeters to over 200 m, depend-
Example: Gossan geochemistry at Ashanti, Ghana.
ing on profile age and tectonic regime.
Where massive sulfide minerals oxidize, the remnants, in-
Under the effects of weathering and transportation of the
cluding ferric oxyhydroxide, jarosite, hematite, and secondary
resulting products, various regolith profiles may develop. In
minerals of metals present in the sulfide zone, may accumulate
respect to the parent material, these profiles can be divided into
to form gossans (Blain and Andrews, 1977). A number of
residual and transported components, containing material of
major mineral deposits have been discovered through the dis-
varying ages and origins as exemplified by some profiles in
covery of gossans (e.g., the Broken Hill Ag–Pb–Zn deposit).
deeply weathered terrains (Figure 10). In such profiles, there
Gossans can be differentiated from other ferruginous regolith
can be several distinct phases of ferruginization, deferruginiza-
materials by their mineralogical and geological characteristics,
tion, kaolinization, silicification, and calcification, each with
trace element geochemistry, and field characteristics of color
the potential to generate a new metal dispersion event or ‘reset’
and texture (Blanchard, 1968; Thornber and Taylor, 1992).
the regolith geochemical patterns. Over the last two decades
Gossan geochemistry can be used to quantify metal retention
regolith-dominated terrains have received considerable explo-
in the regolith and to identify potential exploration options.
ration attention and study as the potential for finding sizeable
At Ashanti, Ghana, chemical weathering of Au-bearing
new mineral deposits becomes greater than in the more
sulfide-rich lodes produced a relict boxwork lattice after sul-
explored outcropping areas. This is largely due to a better
fides now preserved by goethite, hematite, jarosite, and scor-
understanding of the fact that all aspects of the regolith –
odite (Bowell, 1994b). The concentration of Au and pathfinder
distribution, characteristics, processes, and evolution – are
elements was reduced in the gossan as a consequence of
supergene leaching. Despite this, mass balance calculations
Red-brown sandy are able to delineate primary geochemical anomalies even in
Quaternary

clay variably weathered gossan exposures though the proportion

of many elements has been decreased in proportion to the
Silicified, silty to intensity of weathering (Figure 11). Owing to the predomi-
gravelly colluvium
and alluvium
nance of arsenopyrite in the Au-bearing lodes at Ashanti, As,
Transported overburden

Au, and, to a lesser extent, base metal concentrations serve

Pisolitic ferricrete
as reliable criteria in differentiating the gossans.
Mega mottled
paleochannel clays
[M]w / [M]p
Tertiary

Transported gravel
0.0 0.2 0.4 0.6 0.8 1.0
0
Organic-rich soil

Clays Clay-rich soil

20
Base of sediments
Lateritic residuum Gossan

40
Cu
Depth (m)

Mottled saprolite
basement rock

Zn
Regolith on

As
60

Saprolite

Saprock
Bedrock
Figure 10 Generalized regolith profile for the Yilgarn Craton, Australia,
showing a three-layered strato-regolith architecture. Modified from
Cohen DR, Kelley DL, Anand RR, and Coker WB (2010) Major advances
in exploration geochemistry, 1998–2007. Geochemistry: Exploration,
Environment, Analysis 10: 3–16.
80
100 Transition zone
Figure 11 Enrichment factor ([M]w/[M]p) variations with depth in the
gossan and soils from the Justice Mine, Ashanti, Ghana. Modified from
Bowell RJ (1994) Sulfide oxidation and the production of gossans,
Ashanti mine, Ghana. International Geology Review 36: 732–752.
630 Exploration Geochemistry
Example: Regional sediment geochemistry, northern Carlin Belt,
Nevada.
Stream sediments and other drainage materials are com-
monly used in regional reconnaissance geochemical explora-
tion. Providing the selection of sampling methods and
materials is appropriate, they generally reflect the average geo-
chemical composition of weathered materials dispersing me-
chanically and hydromorphically in the catchment (Hale and
Plant, 1994; Hawkes, 1976).
The Carlin Belt of northern Nevada is one of the richest Au
belts in the world, having produced more than 50 Moz. Most
of the precious metal deposits are hosted in decalcified,
silicified, and clay-altered strata below the Roberts Mountains
Thrust (Theodore et al., 2003). Two geological relationships in
Nevada influence the regional geochemical distributions – an
intact lower Paleozoic stratigraphic sequence of siliceous rocks
in the upper plate of the middle Paleozoic Roberts Mountains
Thrust and the widespread repetition of rocks high in the upper
plate developed during the late Paleozoic thrusting that
thickens the cover above mineralization in the lower plate.
District-scale geochemical patterns of several elements in
stream sediments and surface rocks coincide with the north-
ernmost Carlin trend (Figure 12). Elevated As and Sb contents
in stream sediments (up to 54 ppm As) have northwest elon-
gate lobate patterns that outline a ‘chalcophile corridor’ across
a width of approximately 4 km. Arsenic contents of exposed
rocks (up to 90 ppm As) strongly correlate with adjacent
stream sediment geochemistry, but the areal extent of elevated
trace elements in stream sediments (including Sb, Au, and Pb)
is larger than the rock outcrop.
Example: Au dispersion in soils, Ashanti Region, West Africa.
In deeply weathered tropical regolith, hydromorphic disper-
sion may deliver broader and more contiguous anomalies than
clastic dispersion. Chemical weathering occurs at rapid rates in
such environments and, owing to the presence of high anion
concentrations, natural organic acids can dissolve even resistate
minerals, such as native Au (Bowell et al., 1996). This can be
observed in the resulting mineralogy of Au recovered as a heavy
indicator mineral from such profiles (Figure 13). Abundant
natural organic acids and thiospecies deeper in the regolith can
influence Au grain morphology. In the surface soil, fine-grained
Au intergrowths with soil organic matter are common, reflecting
reduction of Au complexes by insoluble organic acids. Within
the saprolite, Au released from the mineralized zone reacts with
ligands preferentially losing Ag and secreting Au back on the
grains to produce an Au-rich rim. These textures are in marked
contrast to hypogene-free Au that is initially liberated at the
protolith–regolith interface and is commonly characterized by
lower fineness and high crystallinity (Bowell, 1992).
13.24.3.3 Transported Cover
Many regions of the world are covered by thick, transported
regolith or young sedimentary rock cover (Figure 10). This
presents special problems for geochemical exploration
methods that use surface samples. Examples of terrains domi-
nated by transported regolith and other materials include the
Mesozoic to Tertiary sedimentary basins of Australia, colluvial
and alluvial basin fill in the southwestern United States and
the Andes, recent volcanic ash in modern volcanic arcs such
as Indonesia, and glaciolacustrine deposits across Canada,
Scandinavia, and Russia. Some of these regions have suffered
underexploration relative to their indicative mineral potential.
Numerous case studies have documented the development
of secondary geochemical dispersion haloes and mineralogical
changes within transported regolith above deeply buried min-
eral deposits in such regolith settings (Butt et al., 2005; Kelley
et al., 2003; Lawrance, 1999; Mann et al., 1998; Smee, 1998;
Wang et al., 1999). There is ongoing debate as to the physical
or chemical mechanisms by which such dispersion proceeds.
Proposed mechanisms include combinations of advection,
groundwater flow, capillary action, diffusion of volatile
compounds, and biological action. Two mechanisms that
have received significant attention over the last decade are
electrochemical dispersion associated with oxidizing sulfide
mineralization and cyclical dilatancy pumping.
Self-potential currents, associated with oxidizing sulfide de-
posits, are the basis for one class of dispersion model in which
the upward movement of electrons in an electrically conductive
sulfide body results from the electrochemical gradients formed
between (underlying) reducing and (overlying) oxidizing envi-
ronments (Bølviken and Logn, 1975; Govett, 1973; Smee,
1983). A revised model (Figure 14) provides for upward prop-
agation of reduced species along the redox gradient to the water
table, forming a reduced column over the mineralized zone and
the development of geochemical anomalies in the overlying
surficial overburden (Hamilton, 1998, 2000). Several detailed
investigations of surficial geochemical responses over deeply
buried sulfide-hosted Au and VMS deposits, in various terrains,
have been conducted to test this model (Cameron et al., 2004;
Hamilton et al., 2004a,b; Mokhtari et al., 2009a).
In tectonically active regions, variations in dilatancy along
faults and fractures have the capacity to physically transport
fluids, including contained metals, through large vertical dis-
tances in a process termed cyclical dilatancy pumping (Sibson,
1981, 2001). Such a model has been used to explain the
development of surface geochemical anomalies in areas with
a thick vadose zone at the Spence porphyry Cu deposit in
northern Chile, which is buried beneath 30–180 m of Miocene
piedmont gravels (Cameron et al., 2002). Copper in ground-
water is restricted to the mineralized area due to the tendency
of Cu2þ released by oxidation of sulfides to adsorb to Fe
hydroxide colloidal particles and coatings, whereas elements
that dissolve as anions (e.g., As, Mo, Se, and Re) were found to
be dispersed widely. Field measurement of the conductivity of
soil–water slurries showed two zones of salt (NaCl) enrich-
ment, one directly over the deposit and the other 1 km away
(Figure 15). Trenching of the soils in these zones revealed
vertical fractures in the gravels, whereas trenching in a back-
ground area showed no fractures. Additional evidence for the
Cu anomalies in soil being related to cyclical dilatancy pump-
ing comes from the presence of atacamite, a secondary mineral
in the oxide zone of many deposits in northern Chile
(Cameron and Leybourne, 2005, 2006).
Example: Dispersion through Mesozoic cover over the Osborne
Cu–Au deposit, Australia.
The Proterozoic Osborne Cu–Au deposit in Queensland is
buried by up to 30 m of Mesozoic sedimentary rocks, and the
entire profile subjected to deep weathering (Rutherford et al.,
2005). Elevated concentrations of Cu and other elements occur
 Exploration Geochemistry 631

Woods
Gulch

Big
Springs

Late Palaeozoic
and Mesozoic rocks

Early Palaeozoic RMT

upper-plate rocks

Palaeozoic RMT
lower-plate rocks

Deposit types
Sediment host Au–Ag
Hot spring Au–Ag
Distal-dissem Ag–Au
Au skarn
Epithermal quartz–alunite
Hg and Sb deposits

−1.8 −1.5 −1.2 −0.9 −0.6 −0.3 0 0.3 0.6 0.9 1.2 Log as Z-score
Figure 12 Distribution of As contents derived from 4300 stream sediment samples for the northern Carlin trend, USA. Modified from Theodore TG,
Kotlyar BB, Singer DA, Berger VI, Abbott EW, and Foster AL (2003) Applied geochemistry, geology and mineralogy of the northernmost Carlin trend
Nevada. Economic Geology 98: 287–316.

in the Mesozoic sedimentary rocks (Figure 16). Aerosols, col-
lected on polystyrene-coated slides placed within traps in shal-
low soils pits, contained elevated values of trace and other
elements directly over mineralization, with some lateral dis-
persion (Figure 17). The patterns indicate both mineral and
salt-bearing volatiles are moving vertically through the regolith
profile.
Example: Dispersion through thick alluvial cover at Mandamah,
Australia.
The subeconomic porphyry Cu–Au Mandamah deposit
(0.3% Cu) is hosted by altered andesitic Siluro–Ordovician
Gidginbung Volcanics (Figure 18). The deposit is overlain by
30 m of in situ (residual) regolith and 50 m of alluvium. The
upper 70 cm of the profile contains discontinuous carbonate-
rich zones. Total and selective geochemical extraction patterns
display no indication of elevated values for the key commodities
in the underlying mineralization (Cu, Mo, or Au), but exhibit
distinct ‘rabbit ear’ anomalies for carbonate-hosted elements (Ca,
Mg, and REE) over mineralization along a number of traverses,
which also coincide with a drop in the electromagnetic response
in shallow alluvium (Mokhtari et al., 2009b). This supports a
component of dispersion by electrochemical processes.
632 Exploration Geochemistry

100
m
Gold anomaly
Surface
cover Mottled
(a) clay
zone
Water table
100 μm

Saprolite

30 – 40 m
Protolith
(b)
Primary mineralization

300 μm
Legend

(c) Chemical mobilization

Physical mobilization
800 μm

Figure 13 Schematic representation of clastic and hydromorphic dispersion in a tropical regolith.

Zone of CaCO3 Zone of metal

accumulation accumulation Upper limit
O2
of carbonate

A horizon

Zn Cd
B horizon
Oxidation zone
Low pH
Carbonate loss
Water table

Clay
Zn2+ Cu2+ Fe2+
Reduced column

Host lithology Sulphide

Figure 14 Redox geochemical dispersion model of Hamilton (1998, 2000) showing the development of a reduced column over sulfides in transported
regolith. Modified from Cameron EM, Hamilton SM, Leybourne MI, Hall GEM, and McClenaghan MB (2004) Finding deeply buried deposits using
geochemistry. Geochemistry: Exploration, Environment, Analysis 4: 7–32.

Example: Geochemical patterns in regolith at Mt. Gibson,
Boddington, and Cobar, Australia.
Fe cemented sediments are generally unsuitable as sample
media on a local scale but may indicate distal mineralization,
either within their detrital component or in the hydromorphically
derived goethite cement or clast rims. The distribution of metals
within various components or facies of regolith profiles is highly
variable. In the vicinity of Mt. Gibson, much of the surficial
ferricrete and lateritic gravels is derived from recemented sands,
and widespread dispersion of Au results in highly elevated values
in the gravels compared with the saprolite (Figure 19). Con-
versely, lateritic gravels at Boddington are mainly ferruginous
lags of local origin and display lower Au values than the saprolite
(Anand, 2005; Anand and Smith, 2005).
Near the CSA Cu–Pb–Zn deposit, Cobar, the basal unit in
the transported regolith is clay and quartz-dominated silts and
the surface layer a mixture of silts and ferruginous lags. Low
concentrations of Fe in the transported silts and clays result in
lower contents of other transition metals (such as Pb), whereas
the ferruginous lags contain high Pb due to the adsorption
onto Fe oxides and subsequent incorporation into the
hematite–maghemite–goethite structure. Elsewhere in the
Cobar area, surface lags contain a wide variety of materials,
including lithic and ferrolithic lags displaying mineral and

Eastern
Ore zone fracture zone
16
Cu (ppm)
8 2001; McClenaghan, 2005). To this end, substantial analysis of
0 flow directions and paleotopography is required as a basis for
2 both sampling and spatial data interpretation.
As (ppm)
1 till geochemistry for minerals such as sulfides and carbonates
0 detected in the fine fraction (typically <2 mm) of weakly oxi-
0.8
Na (%)
0.4
0 rived from drilling, follow-up geochemical surveys for targets
0 500 1000 1500 2000 2500 m
Vertical fracture
in gravels
with saline soil
Figure 15 Copper, As, and Na contents obtained by a weak
geochemical extraction applied to surface regolith collected from a
traverse across the gravel-covered mineralization and adjacent
deep fracture zone, Spence porphyry Cu deposit, Chile. Modified
from Cameron EM, Hamilton SM, Leybourne MI, Hall GEM, and
McClenaghan MB (2004) Finding deeply buried deposits
using geochemistry. Geochemistry: Exploration, Environment, Analysis
4: 7–32.
geochemical features indicative of a local origin and magnetic
lags, which accumulate in drainages and have other features
indicative of both a complex history of formation and poten-
tially extensive transportation. At the Mrangelli base metal
prospect, Cobar, magnetic lags display a more restricted zone
of elevated Zn values around shallow-buried mineralization
than the nonmagnetic ferrolithic lags (Figure 20; Alipour et al.,
1997; Cohen et al., 2005a,b).
13.24.3.4 Glaciated Terrains
Recently glaciated terrains are a specific example of areas with
transported cover. Mechanical processes related to the effects of
ice movement and subsequent reworking of the glacial de-
posits tend to dominate geochemical dispersion, and the
resulting glacial materials more closely reflect the primary
composition or endogenic components of the bedrock source
than regolith materials in other terrains.
Till is the favored sampling medium in much of the
northern hemisphere, particularly in Alaska, Canada, and
Fennoscandia (McMartin and McClenaghan, 2001). Down-
ice dispersion from mineralization tends to generate very
long and narrow trains with the geochemical patterns such as
Exploration Geochemistry 633
the occurrence and abundances of indicator minerals, varia-
tions in Au grain morphology, and concentrations of target
elements dissipating as barren material is added to the glacial
materials (Coker and DiLabio, 1989; DiLabio, 1990; Levson,
glacial sediment stratigraphy and reconstruction of both ice
Postglaciation weathering processes may significantly affect
(Klassen, 2001; Shilts, 1984). Hydromorphic dispersion is best
dized till. At the regional scale, stream and lake sediments have
commonly been used to target mineralized areas (Painter et al.,
1994).
Apart from the analysis of glacial overburden samples de-
such as diamondiferous kimberlites and various metal deposits
include groundwater surveys (Figure 21; Sader et al., 2007),
biogeochemistry (Dunn, 2007), and a variety of soil-based
methods capable of detecting weak dispersion haloes at the
surface resulting from the vertical migration of elements and
their incorporation in secondary minerals such as Mn oxyhydr-
oxides (Hattori et al., 2009).
Example: Diamond exploration using indicator minerals, Ranch
Lake kimberlite, Lac de Gras, Canada.
The Ranch Lake volcaniclastic crater facies kimberlite con-
tains abundant Cr-diopside and pyrope accompanied by
minor ilmenite and chromite. Indicator minerals in the
0.25–0.5 mm size fraction till define a ribbon-shaped glacial
dispersal train trending west for 70 km (McClenaghan et al.,
2002). Near the source, the indicator train is 500 m wide,
whereas 20 km down-gradient, the width has increased to
2000 m (Figure 22). The lateral edge of the train is well
defined by the presence or absence of indicator minerals in
till. The microchemistry of the indicator minerals can be used
further to determine potential of the kimberlites to host
diamonds.
Example: Till geochemistry in the Peräpohja Schist Belt.
In the ribbed moraine terrain of southern Finnish Lap-
land, various depths of till cover the Peräpohja Schist Belt,
and layered intrusions along its southern margin that are
known to host potential Au, Co, Cu, Fe, Zn, U, Ni, and PGE
mineralization (Sarala and Peuraniemi, 2007). High element
concentrations in till can be related to mineralization where
the till is less than 3 m deep. Subglacial gouging of bedrock
favored deposition of rock material in short lateral distances
from the source into till on the surficial parts of the ridges. At
Kuohunki, near the Kuohunkiso mire in the Ranua Rogen
moraine field, a glacial dispersion train 200 m long and
10–20 m wide of U-bearing boulders derived from the local
Archean rocks can be delineated. While the till consists
mainly of sandy layers with large angular boulders, the
<0.06 mm fraction also contains elevated U values (up to
89 ppm U) that correspond with bedrock anomalies of
U-bearing pegmatites and gneiss (Figure 23). The maximum
extent of till U anomalies from a known source in this area is
200 m. The short distance of fluvioglacial transport (<500 m)
is indicated by the angularity of clasts in the area, by the
abundance of locally derived boulders in the till, and
634 Exploration Geochemistry

Fe
<1 %
1–3
3–8
8–15
>15

Cu
<15 ppm
15–50
50–200
200–1000
>1000

100 m

120 m
Mesozoic
cover
80
Proterozoic
bedrock

40
Cu – Au
Mineralization

Figure 16 Distribution of Fe and Cu in a profile through the upper section of mineralization and overlying Mesozoic cover at the Osborne Cu–Au
deposit, Queensland, Australia. Data from Lawrance (1999).

ng cm−1 Ore Ca
20 zone
Cl

10 Mg
Relative response

0
Ce
0.8 Cu

Mo
0.4

0 Cu
0 500 1000 1500 m
Figure 17 Concentration of Cl and Cu in aerosols collected from a
traverse over the deeply buried Osborne Cu–Au deposit, Queensland, 0
Depth (m)

Alluvium
Australia. Data from Rutherford et al. (2005). 50 In situ regolith
100 Volcanic
150 host rock

by the preservation of euhedral pyrite and native Au grains Cu–Mo–Au mineralization

in heavy mineral concentrates. The benefit of the restricted
dispersion is that, despite the extensive till cover, sampling of
the ribbed moraine till from ridgetops can be used effectively
for mineral exploration because they are compositionally
dominated by local bedrock.
and hydrothermal alteration
Figure 18 Potassium acetate-extractable element patterns, with ‘rabbit
ear’ anomalies displayed in the carbonate-hosted elements, over deeply
buried mineralization at the Mandamah Au–Cu(–Mo) porphyry deposit,
NSW, Australia.

Mt Gibson, WA
Lateritic gravels
Lateritic duricrust
Mottled zone
Saprolite
0 1000 2000
Boddington, WA
Lateritic gravels
Lateritic duricrust
Fragmental duricrust
Bauxitic zone
Saprolite
0 1000 2000
Au (ppb)
Figure 19 Examples of variation in trace element concentration distributions and patterns beween different regolith types at Mt. Gibson and Boddington
(WA) and Cobar (NSW), Australia. Modified from Anand RR and Smith RE (2005) Mt. Gibson Au Deposit, Western Australia. In: Butt CRM, Robertson IDM,
Scott KM, and Cornelius M (eds.) Regolith Expressions of Australian Ore Deposits. Perth: CRC LEME, Optima Press; Anand RR (2005) Boddington,
Western Australia. In: Butt CRM, Robertson IDM, Scott KM, and Cornelius M (eds.) Regolith Expressions of Australian Ore Deposits. Perth: CRC LEME,
Optima Press; Shen XC, Cohen DR, and Dunlop AC (1999) Geochemical dispersion in residual and transported regolith along drainage systems near the
CSA Mine, Cobar, New South Wales. In: Taylor G and Pain C (eds) Regolith ’98: New Approaches to an Old Continent, pp. 255–262. Perth: CRC LEME.
13.24.3.5 Other Example Techniques
13.24.3.5.1 Heavy indicator minerals
Heavy and/or resistate minerals can provide a good indication
of primary geology and the presence of some types of mineral
deposits (Averill, 2001). The effectiveness of heavy indicator
mineralogy is dependent on the minerals being source-specific
and having useful properties that complement their high spe-
cific gravity. In the case of kimberlites, the indicator minerals
need to be found in a limited number of rocks other than
kimberlite; be relatively resistant to weathering such that a
reasonable dispersal train can be formed in sediments or soil;
be sufficiently abundant; and be visually distinct or amenable
to concentrating so that they can be detected, characterized,
and relative abundances determined. Such minerals can pro-
vide an indication of bedrock geology type. For example, com-
pilations of geochemical data found in the heavy mineral
fraction of laterites from Brazil and the Philippines have been
used to determine the protolith geology underlying the laterite
profiles (Friedrich et al., 1992).
Typically coarse-grained indicator minerals can be used to
identify three major mineral deposit types: (1) gold deposits in
which Au is present as native Au in the primary material or is
able to form secondary Au in the regolith; (2) kimberlite-
associated minerals (KIMs), enriched in Mg and Cr; and (3)
metamorphosed or magmatic massive sulfide indicator
minerals (MMSIMs) (see Couriveau and Spry, Chapter 13.7)
that are enriched in Mg, Mn, Al, and Cr (Averill, 2001). The
source of MMSIMs can be related to different mineral deposit
types, each with their own unique signature (Table 1). This
includes volcano-sedimentary massive sulfides (which encom-
passes volcanogenic, sedex, and Mississippi Valley subtypes) in
medium- to high-grade metamorphic terrain skarns or greisen
Exploration Geochemistry 635
CSA, NSW Fe (%)
Fe Pb (ppm)
0 15%
Pb
0 25 ppm
0m
Coarse
silt + lag
Transported
silt + clay
Saprolite
Chesney
Siltstone
Girilam-
bone Gp.
60
deposits and magmatic Ni–Cu sulfides. Mineralogical analysis
of such concentrates can provide additional information to
chemical analysis, including distance to source of dispersal by
assessment of wear of the grains – for kimberlite exploration,
distinguishing diamond bearing from nondiamond bearing
pipes (Gurney and Moore, 1993). In the case of Au grains,
the anomaly signature in the concentrate is both geochemical
(or analytical) and mineralogical (or visual). In the case of
KIMs, it is generally only mineralogical because of the limited
numbers of recovered indicator grains enriched with Mg and
Cr and the fact that these elements are also present in the
higher volume nonindicator mineral fraction.
Heavy indicator mineral exploration for Au deposits is
common, and historically many deposits have been found by
panning and following an indicator dispersal train in streams to
the endogenic or primary source. Such studies have occurred
globally in virtually all environments, including shallow ma-
rine sediments. The conditions under which Au is solubilized in
the regolith tend to be rare (Bowell, 1992; Hough et al., 2009;
William-Jones et al., 2009). Hence, most Au geochemical
anomalies are related to native Au or Au alloys rather than
chemically adsorbed Au in soils and sediments, although in
organic-rich soils Au may be present as colloids. Being soft and
malleable, Au grains are deformed during transportation from
pristine to modified and reshaped forms and both the form and
abundance of Au nuggets may be useful indicators of proximity
to the mineralized source (Minter et al., 1993).
13.24.3.5.2 Hydrogeochemistry
Analysis of aqueous solutions to determine potential geochem-
ical anomalies has been applied globally and represents a
potentially powerful mineral exploration tool (Giblin and
Mazzucchelli, 1997; Kirste et al., 2003; Leybourne and Cameron,
636 Exploration Geochemistry

>150 ppm
Zn 50–100
0 1000 m
Bedrock Zn anomaly

Magnetic lag
22
5m
220 m

215 m

Nonmagnetic lag

Figure 20 Zinc patterns in magnetic and nonmagnetic lag at the Mrangelli base metal prospect, Cobar, NSW, Australia. Modified
from Alipour S, Cohen DR, and Dunlop AC (1997) Geochemical characteristics of lag in the Cobar Area N.S.W. Journal of Geochemical
Exploration 58: 15–28.

2010; Pirlo and Giblin, 2004). The benefits of sampling

Waters in Non-kimberlite Reaction
this medium are that groundwaters are generally chemically
kimberlite groundwaters modelling reactive with mineralization and host rock, particularly where
B30 Diamond Lk with kimberlite waters are oxygen-bearing, and this improves methods of anal-
95-2 Country rock mineral suite
ysis and sensitivities in element analysis for trace elements
C14
A4 including Au and nontraditional isotopes such as those of
Diamond Lk Cu. Where groundwater recharges to depth, it may contact bur-
6 1:1 and 10:1 water–rock ratio ied mineralization and react to deliver a chemical signature that
can be used to delineate and quantify protolith mineralization.
5 100:1 water–rock ratio
Where groundwater is flowing away from bedrock miner-
alization, it provides a potentially broader exploration target
4
than lithogeochemical dispersion (Figure 24). Sample prepa-
Log10 (K/Mg)

3 ration is relatively simple and background concentrations for

many elements of interest are generally low, enhancing geoche-
2 mical contrast. Hydromorphic dispersion of chemical elements
into soils and sediments can generate extensive geochemical
1
haloes (Cameron et al., 2004; Eppinger et al., 2007).
500:1
0 Water–rock ratio
Example: Hydrogeochemical exploration for Au, St. Ives Goldfields,
Australia.
-1 In a hydrogeochemical survey conducted over the St. Ives
1000:1
-2
Water–rock ratio area of the eastern Goldfields, >80 drill holes were sampled on
6 7 8 9 10 11 12 13 a kilometer-spaced grid (Carey et al., 2003). Hydrogeological
pH data were used to indicate direction of flow. Regional brines
flow toward the salt lake where evaporation occurs and the
Figure 21 Plot of pH versus K/Mg for ground waters in the vicinity of the
resulting hypersaline brines sink and flow away from a lake
C4, Diamond Lake and 95–2 kimberlites and nonkimberlitic areas, Ontario,
beneath the regional brines. Groundwater Au values up to
Canada. Modified from Sader JA, Leybourne MI, McClenaghan MB,
and Hamilton SM (2007) Low-temperature serpentinization processes 0.52 mg l1 are located in close proximity to the dolerite-
and kimberlite groundwater signatures in the Kirkland Lake and Lake hosted, orogenic lode Junction Au deposit (Figure 25). In
Timiskaming kimberlite fields Ontario, Canada. Geochemistry: Exploration, the deeper brines, there were no elevated Au values close
Environment, Analysis 7: 3–21. to the Argo/Apollo Au deposit; however, shallow regional
 Exploration Geochemistry 637

65⬚ 19¢

111⬚ 59¢

Ranch Lake
kimberlite

No. Cr-diopside
per 20 kg sample
0
1–10
11–50
51–150
151–300

111⬚ 26¢
301–545
65⬚ 11¢
Canamera Till sample
5 km
Figure 22 Distribution of Cr-diopside, a kimberlite indicator mineral, in selected Canamera Till samples (0.42–0.84 mm) collected up-ice and down-ice
(west) of the Ranch Lake kimberlite, NWT, Canada. Modified from McClenaghan MB, Ward BC, Kjarsgaard IM, Kjarsgaard BA, Kerr DE, and Dredge LA
(2002) Indicator mineral and till geochemical dispersal patterns associated with the Ranch Lake kimberlite, Lac de Gras region, NWT, Canada.
Geochemistry: Exploration, Environment, Analysis 2: 299–321.

groundwater anomalies observed in the study indicated that

17
2m

hydrogeochemical exploration in the Yilgarn may be effective

U mineralization at a resolution of 0.5–4 km spacing.
Example: Hydrogeochemical exploration of Spence deposit, Chile.
Porphyry Cu deposits are associated with intermediate to
felsic intrusive rocks. Some of the largest deposits are located in
Chile. Key geochemical characteristics include anomalous ac-
cumulation of As, Mo, Se, and Re in addition to Cu.
17
8m At the Spence deposit (Section 13.24.3.3), groundwaters
175
m show variable chemistry, indicating two end-members, a rela-
tively fresh groundwater with TDS <1000 mg l1 and a saline
end-member with TDS >30 000 mg l1 (Leybourne and
172 m

172 m
m
175

Cameron, 2006a). The saline end-member has a composition

that indicates interaction with the Spence porphyry (Figure 26).
175

17 0 100 m
5m
m

Upslope of the Spence deposit, groundwaters have low

Boulder lithology concentrations of porphyry Cu-related species, such as Cu,
Till
Swamp / mire
Mo, Se, Re, and As. The sulfate has isotopic compositions
U-bearing biotite–apatite gneiss
typical of salars and nonmineralized groundwaters of the
U-bearing granites and pegmatites Glacial flow
U-bearing gneiss–granite and gneiss Atacama Desert. Oxygen and hydrogen isotopes of these upflow
direction
Sulfides waters are consistent with recent recharge at elevations around
4000 m in the high Andes. Within the deposit, As, Se, Re, and
Figure 23 Distribution of U-bearing boulders on ribbed moraine ridges
Mo contents increase and remain elevated above background
and the location of U mineralization near the Kuohunkisuo mire,
Kuohunki, Finland. Modified from Sarala P and Peuraniemi V (2007)
>2 km down-gradient from the deposit as, under the prevail-
Exploration using till geochemistry and heavy minerals in the ribbed ing Eh–pH conditions of groundwater (neutral, mildly
moraine area of southern Finnish Lapland. Geochemistry: Exploration, oxidizing), all these elements form oxyanions that are stable
Environment, Analysis 7: 195–205. in solution and less readily adsorbed onto oxyhydroxides and
clay minerals. Down-gradient, the water table shallows to a
brines displayed high Au downstream. This is attributed to salar and the sediments are strongly enriched in these elements
the displacement of local groundwater by hypersaline brines (Leybourne and Cameron, 2006b). By contrast, Cu is anoma-
from Lake Lefroy. Pathfinder elements, such as Sb, Bi, and lous in the vicinity of the Spence deposit but rapidly decreases
Te, were generally below the detection limit. Evaluation of down-gradient, owing to lower solubility at the prevailing
638 Exploration Geochemistry

Table 1 Heavy indicator mineral element signatures mobility of elements in the surface environment. Whereas
processes such as methylation of metals may increase mobility,
Deposit type Indicator minerals Indicator incorporation into cells reduces mobility. Significant accumu-
elements
lation of Au in macrofungi and ectomycorrhizae indicates in-
Gold Native Au, electrum Au, Ag volvement in the cycling of Au within the soil (Borovička et al.,
Kimberlites Diamond C (N, B) 2010). Microbial activity influences the mobility of nearly every
Pyrope garnet Mg, Al, Cr, Ti element, including Au and As in soil (Reith and McPhail, 2007).
Mg-ilmenite Mg, Ti, Cr, Mn, Al Bacteria such as Thiobacillus ferrooxidans are used in a number of
Cr-diopside Ca, Mg, Cr, Al, Na ore processing and soil remediation systems (Watling, 2006).
Cr-spinel Mg, Cr, Al, Mn, Ti Conversely, the characteristics, distribution, and biochemistry
Forsterite Mg, Ni, Mn of biota may be affected by mineralization due to the release of
Volcano-sedimentary Tourmaline group Al, B, Mn, Ni, Mg,
metals and localized changes to soil pH and Eh.
massive sulfide minerals Cu
A large number of studies demonstrate geochemical re-
Dumortierite Al, B
Mn-epidote Mn sponses in plants and other biota to nearby mineralization
Spessartine Mn, Al (Anand et al., 2007; Arne et al., 1999; Cohen et al., 1998, 1999;
Gahnite Zn, Al Dunn, 2007; Lintern, 2005). At the McKinnons Au deposit in the
Franklinite Zn Cobar area of NSW, a 500-m-wide zone of Cypress pines displays
Willemite Zn distinctly elevated Au and As values in the needles (phyllodes)
Cr-rutile Cr compared with a narrower zone containing some elevated Au
Barite Ba values but a lack of As response in the adjacent soils (Figure 27).
Chalcopyrite Cu Termitaria are a distinctive feature across much of the semi-
Cinnabar Hg
arid tropical savannah of South America, Africa, Southeast
Loellingite As
Asia, and Australia and are the product of the burrowing activ-
Native Au Au
Skarns Forsterite–knebelite Mg, Mn ities of termites. They provide a useful medium for exploration
olivine geochemistry, even at regional scales, due to their widespread
Vesuvianite Mg geographical occurrence and the great depths from which reg-
Grossular garnet Al, Cr olith particles are brought to surface by the termites (including
Scheelite W potential development of secondary geochemical anomalies
Chalcopyrite Cu derived from those materials). An important feature of termi-
Greisen Topaz Al, F taria is that termite species tend to be territorial and thus the
Fluorite BF geochemical signature of the mounds is from material proxi-
Tourmaline group Al
mal to the mound. Studies in Zimbabwe indicate termites
minerals
burrow to the water table to a depth of up to 30 m deep
Cassiterite Sn
Wolframite W (Brooks, 1982), although depths of 5–15 m are more common
Chalcopyrite Cu (Petts et al., 2009).
Magmatic Ni–Cu ores Chromite Al, Cr, Mg
Olivine Mg 13.24.3.5.4 Vapor and gas geochemistry
Orthopyroxene Mg, Cr There is potential to measure direct indicators such as volatile
Uvarovite garnet Cr elements, species, and aerosols emanating from buried de-
Chalcopyrite Cu posits (including Hg, Rn and a variety of metal halides,
Pentlandite Ni carbonyls, and organometallic species) as well as indirect
Pyrrhotite Ni
indicators, such as changes to soil CO2/O2 ratios or the abun-
PGE alloys PGE, Au, Bi, Te
dance of various hydrocarbons stemming from redox and
Source: Averill SA (2001) The application of heavy indicator mineralogy in mineral acid–base reactions related to sulfide oxidation or biological
exploration, with emphasis on base metal indicators in glaciated metamorphic and interactions with mineralization (Highsmith, 2004; Klusman,
plutonic terrain. In: McClenaghan MB, Bobrowski PT, Hall GEM, and Cook SJ (eds.) 1993; Polito et al., 2002; Rutherford et al., 2005). The stability
Drift Exploration in Glaciated Terrains. Geological Society Special Publication 185, pp. and mobility of such gases and volatiles is dependent on
69–82. London: Geological Society of London; McClenaghan MB, Bobrowski PT, Hal groundwater and regolith geochemistry, and even barometric
GEM, and Cook SJ (eds.) (2001) Drift Exploration in Glaciated Terrains. Geological pressure. Major faults and lithological boundaries can also
Society Special Publication, vol. 185. London: Geological Society of London. exert significant influence on soil gas geochemical patterns
and mineralization. In an extensive study of a number of Au
Eh–pH conditions. Both studies demonstrate that knowledge of
and base metal mineral deposits in Australia by Carr et al.
site hydrogeology is essential in order to interpret local hydro-
(1986), elevated regolith Hg concentrations were present di-
geochemical anomalies (Leybourne and Cameron, 2010).
rectly over mineralization at some deposits, but with little
evidence of significant lateral dispersion (Figure 28).
13.24.3.5.3 Biogeochemistry Example: Light gas exploration, Junction Au deposit.
Biota exert a major influence on the geochemistry of the A soil gas survey completed across the Junction Au deposit
surface environment and on weathering processes through (Polito et al., 2002) detected strong, broadly coincident CO2–
the release of metabolic and decay by-products, including O2–light hydrocarbon anomalies through sedimentary cover
organic acids and complexing agents (Gadd, 2007; Southam above mineralization (Figure 29). By contrast, only CO2–O2
and Saunders, 2005), affecting the form, distribution, and anomalies were observed in areas having no Au but containing
 Exploration Geochemistry 639

Surface Drill holes

4 3
Precipitation 2
1

Gold Water ta
b le
deposit

Water Thinly covered

flow pediment area

Deeper
gravel
Ore filled
deposit basin

Oxidation of ore deposit contributing trace elements to passing groundwater

Figure 24 Schematic representation of trace element halo generated by groundwater leaching of orebodies.

50 ppt 30 ppt

St Ives Au orebodies
mill Sampling wells
50 ppt Au
40 ppt Au
Argo / Apollo 30 ppt Au
20 ppt Au
10 ppt Au
Diana

Lake
Lefroy

Junction Boulder - Lefroy

Fault

Lake
N Finn
Tramways
2 km complex

Figure 25 Gold distribution in a regional hydrogeochemical survey, the St. Ives ore, WA, Australia. Modified from Carey ML, McPhail DC, and Taufen
PM (2003) Groundwater flow in playa lake environments: Impact on Au and pathfinder element distributions in groundwaters surrounding mesothermal
Au deposits, St Ives area, Eastern Goldfields, Western Australia. Geochemistry: Exploration, Environment, Analysis 3: 57–71.

carbonate and sulfide mineralization. Oxidation of the mineral
assemblage associated with Au mineralization and the release
of the gases in the fluid inclusions associated with them are
proposed as the sources of the anomalies. The broadly coinci-
dent ΔCO2–ΔO2–light hydrocarbon anomalies indicate that
the anomalies were formed by gas migrating along microfrac-
tures within the shear zone. Weathering of gangue mineralogy
in the altered wall rock produced only ΔCO2–ΔO2 anomalies
with light hydrocarbons detected coincident to the shear zone
structure.
13.24.4 Regional Geochemical Mapping
Multielement geochemical surveys, principally involving
stream sediments or soils, continue to be a cornerstone of
regional mineral exploration. The development of large-scale,
regional reconnaissance geochemical exploration surveys in
the west originated with the NURE program in the United
States (Smith, 2009), the NGR program in Canada (Coker
and Ellwood, 1981), and the Wolfson Geochemical Atlas in
the United Kingdom (McGrath and Loveland, 1992) and has
640 Exploration Geochemistry

NaCI eq % A 80
1.50–3.80
Soil depth
0.43–1.26 15 cm
60
0.02–0.28 30 cm

Hg (ppb)
40
Saline Meteoric
20
ow
Fl
0 Gossan
Mixed
0 500 1000 1500 2000 m
Figure 28 Mercury contents of shallow soils from a traverse over the
Elura Ag–Pb–Zn deposit, Cobar, NSW, Australia. Modified from Carr GR,
Wilmshurst JR, and Ryall WR (1986) Evaluation of mercury pathfinder
1 km
techniques – Base-metal and uranium deposits. Journal of Geochemical
Exploration 26: 1–117.
Figure 26 Plot showing meteoric, saline, and mixed groundwaters
around the Spence porphyry Cu deposit, Chile. Shaded area is the 3000
orebody near the gravel contact. Modified from Cameron EM, Leybourne Δ carbon dioxide (ppm)
2000
MI, Reich M, and Palacios C (2010) Geochemical anomalies in northern
Chile as a surface expression of the extended supergene metallogenesis 1000
of buried copper deposits. Geochemistry: Exploration, Environment,
Analysis 10: 157–169. 0

150

Ore Cypress pine Methane (ppmv)

100
zone needles
50
0.30 6
0
Mine bund
Alluvium, calcrete and overlying saprolite
0.15 3
BFB
Junction
N75 Porphyry?
Dolerite
0.00 0
Figure 29 Soil gas CO2 and CH4 emission profile along a traverse over
As Soil Au the Junction Au deposit, Australia. Modified from Polito PA, Clarke JDA,
(ppm) 30 20–30 cm depth 12 (ppb) Bone Y, and Viellenave J (2002) A CO2–O2–light hydrocarbon–soil-gas
anomaly above the Junction orogenic gold deposit: A potential,
alternative exploration technique. Geochemistry: Exploration,
Environment, Analysis 2: 333–344.
15 6
The most recent release has been the FOREGS Geochemical
Atlas of Europe (Salminen et al., 2005) in which 800 sites were
sampled for soils, floodplain sediments, stream sediments, and
0 0
waters, yielding a density of about one site per 5000 km2. De-
0 400 800 1200 1600 m
spite 250 years of industrialization (including smelting opera-
Figure 27 Comparison of Au and As values in Cypress pine tions) and high variability in the nature of the regolith (from
(Callitris glaucophylla) needles and adjacent soils over the McKinnons Au residual regolith to glacial sediments), the dominant control on
deposit, Cobar, NSW, Australia. Modified from Cohen DR, Shen XC, Cu and most other elements in the topsoil and subsoil over large
Dunlop AC, and Rutherford NF (1998) A comparison of selective
areas is the underlying geology (Figure 30).
extraction soil geochemistry and biogeochemistry in the Cobar Area,
The sampling scale, both coverage and density of samples,
NSW. Journal of Geochemical Exploration 61: 173–190.
and sampling media have a major influence on the scale of
continued into recent times with the geochemical mapping of geochemical patterns that can be measured. Low density re-
China (Li and Wu, 1999; Xie and Cheng, 1997) and other gional soil sampling, on the order of one sample per 100 km2,
countries or provinces. These surveys were mainly designed has traditionally been viewed as offering a low probability of
to support mineral exploration, although regional geochemical detecting small zones of mineralization or contamination
surveys are now being undertaken for environmental purposes (Smith and Reimann, 2008), as the ‘influence’ of a given point
(Darnley et al., 1995; Plant et al., 2003). may extend only a few hundred meters. However, some studies
 Exploration Geochemistry 641

Cu in topsoil Precambrian Terrane

Precambrian Terrane (covered)
Aqua regia / ICPOES Scandinavian Caledonides
837 samples Irish-Scottish Caledonides
Eastern Avalonian Terranes
0 500 km Variscan Terranes
Variscan Gondwana
-1
Cu (mg kg ) Alpine Orogen

3
4
6
8
12
East
16
European
20
Platform
27
43

1
3
5
8
11
15
19
24 Iberia
29
34
40
47
54
61
69
240
Major Cu deposits

Figure 30 Copper in topsoil from the Geochemical Atlas of Europe, along with simplified geological terrane map. Modified from Salminen R, Batista
MJ, Bidovec M, et al. (eds.) (2005) The Geochemical Atlas of Europe. Espoo, Finland: Geological Survey of Finland; Plant JA, Klaver G, Locutura J,
Salminen R, Vrana K, and Fordyce F (1997) The Forum of European Geological Surveys Geochemistry Task Group inventory 1994–1996. Journal of
Geochemical Exploration 59: 123–146.

show that even low density sampling may have a high rate of
detection of known mineralization (Reimann et al., 2007).
Stream sediments provide a greater chance of detection at
such a sampling scale than soils as the material represents an
integration of regolith within the local catchment. Changing of
sampling scale is common in mineral exploration, typically
commencing with low density stream sediment surveys and
progressing to high density stream sediments or soil surveys as
areas of high prospectivity are identified.
Example: Soil geochemical mapping in Cyprus.
Geochemical patterns derived from the multielement anal-
ysis of 5500 soil samples collected in a near-regular grid
at 1 km spacing across the Republic of Cyprus demonstrate
the close control of geology on regolith geochemistry (Cohen
et al., 2011, 2012). Apart from the low-Cu ultramafic core,
there are elevated Cu contents throughout the Troodos Ophio-
lite complex with highest values in the pillow basalts that form
the margin of the TOC. However, elevated values for a linear
combination of Ag, As, Cu, In, and Zn provide a strong spatial
correlation between soil geochemistry and the location of
major Cyprus-type Cu deposits or associated mineral proces-
sing facilities (Figure 31).
13.24.5 Analysis
In exploration geochemistry, most analytical methods seek
to isolate or enhance the geochemical component of the
selected sampling media that is related to the effects of min-
eralization. Therefore, a key component of exploration geo-
chemical program design is the choice of analytical method,
especially the selection of geochemical extraction prior to
determination. Elements in soils are present in various min-
eralogical forms – major components of minerals (e.g., Fe in
goethite or Ca in carbonates), trace substitution (i.e., Zn for
Ca in carbonates), and nonspecific forms (Cu adsorbed to Fe
oxides and U adsorbed to organics). Interpretation of the
distribution of trace elements is therefore also dependent on
the abundance of host minerals for which the analysis of the
major cation in those minerals can stand as a proxy. Other
parameters are also important to measure, such as pH, which
strongly influences the form, solubility, mobility, adsorption
potential, and availability of most elements (McBride, 1994).
Recent developments in selective geochemical extractions
and the implementation of large-scale multielement geochem-
ical surveys have been largely supported by the provision
of high-speed, low-cost, semiautomated, multielement geo-
chemical analyses (Cauglin, 2007). These are largely centered
on inductively coupled plasma mass spectrometry (ICP-MS),
with the support of X-ray fluorescence (XRF) and instrumental
neutron activation analysis (INAA). The basis of these methods
with some geological applications is described in various
texts (e.g., Beckhoff et al., 2006; Hill, 2006). Typical detection
limits for aqua regia ICP-MS/OES are compared with XRF
and INAA in Figure 32. New exploration techniques using
isotope analysis are becoming feasible due to the increasing
availability of high-resolution analytical devices, such as multi-
collector high-resolution ICP-MS. Various applications of
isotopes in detecting buried mineralization are outlined in
Andrew et al. (1998).
Developments in field-portable XRF permit rapid in situ
analysis of major elements and a wide range of trace elements
in rock and regolith at concentrations down to the low ppm
range (Bowell et al., 2011, 2012; Coker, 2010; Glanzman and
642 Exploration Geochemistry

Top soil Cu (ppm)

(0 – 25 cm) TOC
800
TOC 220
Troodos 135
Ophiolite 115
Aqua regia / 100
ICP-MS Complex 75
(TOC) 65
55
45
5377 sites 35
15

Circum-Troodos
Sedimentary Succession

Uncle Charles Skouriotossa Kokkinoyia and Peristerka,

and Kinousa Alestos Kokkinopesula Pytharochoma,
Limni and and Memi Kokkinonero and Ag*As*Cu*In*Zn
Evloymeni Kapedhes index
Mathiati South UN 3000
buffer 1000
zone 500
Apliki 100
60
Agrokipia
40
Sha 20
10
5
Kalavasos Pillow lavas 3
1
Cu Mines

Maghaleni
0 10 20 km

Figure 31 Comparison between aqua regia Cu contents of topsoils (0–25 cm depth) and an Ag–As–Cu–In–Zn index, together with the location of the
major Cyprus-type Cu deposits and host pillow basalts in the Troodos area, Cyprus.

Closs, 2007), allowing detailed spatial mapping of major and
trace element geochemicals at the outcrop scale.
In response to new models that account for the develop-
ment of weak dispersion haloes in transported cover, various
selective geochemical extractions have been used to isolate
geochemical signals associated with specific mineral compo-
nents or element forms in regolith. These are designed to
physically separate the low levels of trace elements contributed
to overburden by various secondary dispersion mechanisms,
and associated with transient mineral phases in the regolith,
from the trace element contents inherited from the transported
cover itself. A number of case studies are presented in Hall
(1998).
A general relationship between some common extractions
and the mineral components they theoretically attack is pre-
sented in Figure 33 (Gray et al., 1999). Whereas most studies
have tended to be empirical investigations of the selective
extraction response of regolith components to deeply buried
underlying mineralization (orientation studies), there has
been limited work on the actual mechanisms of the extractions
or the mineralogical–digestion response relationship (Cave
et al., 2004; Dalrymple et al., 2005). Extraction methods typi-
cally involve various combinations of acids, chelants,
reductants, and exchangeable ions.
One feature common to selective extraction data, though
usually more evident in the less vigorous digestions, is the high
degree of spatial variability over small distances, and this prob-
ably reflects the distribution of the migration paths (fractures
and other discontinuities in the regolith) within which ele-
ments may concentrate, producing discrete anomalies within
surface transported regolith until subsequent processes later-
ally redistribute those transported elements. Conversely, one
effect of buried mineralization may be to take a relatively
uniform initial element distribution in transported regolith
cover and induce ‘geochemical mottling’ through the various
processes described earlier (i.e., an increase in spatial variance
within the regolith without altering the bulk composition of
the block of regolith overlying the mineralization).
Despite the availability of a large array of selective extrac-
tions, aqua regia remains the most common acid leaching
method in geochemistry. Aqua regia rapidly leaches most ex-
changeable elements, dissolves sulfides, carbonates, and nearly
all secondary minerals derived from weathering (including the
main hosts to ore-related metals, such as Fe and Mn oxides), and
delivers a relatively reliable ‘end point’ to extractions.
In all cases, the need for quality control and error estima-
tion in geochemical exploration, from sampling to chemical
analysis, remains critical in exploration geochemistry (Ramsey
et al., 1992; Stanley and Lawie, 2007). Poor sampling options
or methods will negate refinements in analytical and data
processing methods. Robust protocols are required to establish
the accuracy and precision of analysis and to detect sample
contamination or other artifacts in datasets, especially in the
case of selective geochemical extractions where minor changes
in extraction conditions can have severe effects on sample
behavior (Figure 34; Dalrymple et al., 2005).
Example: Nontraditional isotope for mineral exploration: use of
copper isotopes in Iran.
The oxidation of chalcopyrite in a porphyry environment
and formation of supergene-enriched zones of chalcocite
 Exploration Geochemistry 643

100 Fe,Ti
Mn
Al,K
S Ca
10 Sr Na,P Mg
Cu,Y Ba Cr

XRF or INAA (ppm)

Zn Br V
Cd Sn Ni La
1 Ce Be Ga,Ge,Nb,Se
Pb As,Co,Hf,Th
Bi,Cs, Zr
0.1 In,Nd U,Yb
Mo Rb

0.01 Sc, other REE

Tl Lu
Au
Ta
0.001
0.001 0.01 0.1 1 10 100
ICP-MS or
Ir, Ag Hg Sb,Te Li,W B,Hg ICP-OES
Re -cv (ppm)
Suite not routinely analysed by XRF or INAA

Figure 32 Typical detection limits for commercial ICP-MS or ICP-OES vs XRF analyses or INAA. Lower detection limits are available using specialist
techniques, such as hydride generation for As and Te, or prompt gamma INAA techniques.

Increasing proportion of total mineral + metal content dissolved

Adsorbed
Soluble Mn oxides Resistate
+ Crystalline
Carbonates and Silicates
phases exchange Fe oxides minerals
am. Fe ox.
species

Distilled water
MMI
NH4-acetate
Acetate / acetic acid

Inc Enzyme Leach /H2O2

rea Weak NH2OH
sin
g‘ EDTA + HCl
str
en
gth Strong NH2OH
’o
fd Regoleach
ige
sti
on Dilute HCl
Aqua regia
Mixed acids
HF / fusion

Figure 33 The relationship between various selective geochemical extractions and the extent of regolith mineral components attacked. Modified
from Gray DJ, Wildman JE, and Longman GD (1999) Selective and partial extraction analyses of transported overburden for gold exploration in the
Yilgarn Craton, Western Australia. Journal of Geochemical Exploration 67: 51–66.

occur in response to water table fluctuations with precipitation
of chalcocite in the reduced zone beneath the water table.
Oxidation reactions result in isotopic fractionation such that
oxidized Cu in solution is isotopically heavier than the
mineral from which it was derived by low-temperature reac-
tions involving chalcopyrite dissolution (Seo et al., 2007).
Leached zones tend to be isotopically lighter and supergene
zones isotopically heavier than the protolith or hypogene
precursor ore.
To assess the benefit of Cu isotope fractionation in the
delineation of porphyry Cu deposits, the Cu isotope ratios
and Cu concentrations have been measured in oxide and sul-
fide minerals from leached cap, supergene sulfide, and hypo-
gene sulfide zones of the Chahfiroozeh, Darrehzar, Iju, and
644 Exploration Geochemistry

Relative Mn
extraction

1.0
0.8
0.6
0.4
0.2
2

10
1

0
60
pH
)
0 (⬚C

20
p
T em 0.9
0.8
Relative Mn 0.7
extraction 0.6
0.5
1.0 0.4
0.8 0.3
0.2
0.6 0.1
0.4
0.2
1

10
[N
H 0.1

0
60
2O
H– )
HC 0.01 (⬚C
20

p
I] Tem

Figure 34 The Mn extraction response surfaces from a central composite design model under variation in digestion pH, temperature, and
concentration of hydroxylamine–HCl. Modified from Dalrymple IJ (2007) An Approach to the Optimization of Partial Extractions for Geochemical
Exploration. PhD Thesis, University of New South Wales.

Parkam porphyry Cu deposits in the Kerman porphyry Cu belt
of Iran (Mirnejad et al., 2010). In general, d65Cu shows distinct
values of 0.23 to 0.79% in hypogene minerals, 2.52 to 4.82%
in supergene zone sulfides, and 1.0 to 6.16% in leached
cap minerals. Leached cap minerals contain less Cu than su-
pergene and hypogene minerals (Figure 35). The study con-
firmed experimental work and demonstrated that the
weathering and oxidative dissolution of Cu sulfide minerals
generate isotopically heavier fluids and lighter residual min-
erals. When the fluids migrate into reducing zones, the oxi-
dized solutions precipitate Cu sulfides in the enriched zone.
The degree of isotopic separation and concentration differ-
ences is a function of the weathering processes and higher
isotopic signatures in the leach cap of different deposits may
be indicative of higher grade at depth and thus the method
has some potential to assist in refining exploration evaluation
of a deposit.
13.24.6 Geochemical Data Interpretation
There are various approaches to the detection of geochemical
patterns that can be spatially related to mineralization. A di-
chotomy continues to exist between stochastic modeling, ex-
emplified by techniques such as factor analysis (Reimann et al.,
2002) or fractal and related analysis (Cheng et al., 1994; Li
et al., 2004; Shen and Cohen, 2005) and deterministic model-
ing applied to geochemical data.
The traditional approach to the interpretation of explora-
tion geochemical data has been to define a ‘background’ pop-
ulation derived from the characteristics of the actual data
collected or a set of samples known (or presumed) to be
unaffected by mineralization. Thresholds are subsequently
set, beyond which observations are considered ‘anomalous’
(either high or low). Data may also simply be clustered with
the assumption that the more highly populated groups reflect
regional-scale geological processes and the small clusters are
likely to contain samples affected by mineralization. A number
of inherent problems have been identified in such an ap-
proach, especially for large areas where geology, regolith, and
landscape vary substantially (Reimann and Garrett, 2005) as
they fail to recognize that geochemical background varies at all
scales (Reimann and de Caritat, 1998), from continents down
to individual minerals. Recent experience with selective geo-
chemical extraction data suggests the notions of ‘background’
and ‘anomalous’ be abandoned in favor of recognizing that
the multifaceted geochemical characteristics of a suite of
samples reflect the influence of a large number of complex
interacting processes (ancient and modern). The multivariate
characteristics of a dataset are as important as the univariate
ones (Filzmoser et al., 2005), and samples displaying the geo-
chemical or mineralogical effects of mineralization may lie as a
subcluster within the main cluster of observations.
Isolation of complex patterns of correlation between vari-
ables, associations among samples, and the identification of
mineralization-induced effects in data through conventional
multivariate parametric statistical procedures may be biased or
 Exploration Geochemistry 645

8000

ne ne
Su ed
zo rge
h
ac

pe
Le
Chahfiroozeh
6000 Iju
Parkam

Cu (ppm)
Darrehzar

4000

2000

0
-20 -15 -10 -5 0 5 10 15
d 65Cu
Figure 35 Plot of d65Cu versus total Cu for various deposits in the Kerman porphyry Cu belt, Iran. Only samples from the supergene and leached zones
are plotted. Modified from Mirnejad H, Mathur R, Einali M, Dendas M, and Alirezaei S (2010) A comparative copper isotope study of porphyry copper
deposits in Iran. Geochemistry: Exploration, Environment, Analysis 10: 413–418.

1.2 Cu Cu 800
ppm Enzyme leach Aqua regia ppm

0.0 0

1.0 As
ppm Enzyme leach

0.0

0.8
As 7-point Average
Enzyme leach moving
filter Variance

0.0

Gravel Libra zone Virgo zone

2600
Elevation (m)

Porphyrytic andesite
2400
Supergene enrichment
Monzonite porphyry
2200
0 500 1000 1500 2000 2500 3000 3500 m

Figure 36 Comparison of enzyme leach-extractable Cu and As and a seven-point moving average and moving variance for As, from a traverse over
buried mineralization at the Chimborazo deposit, Chile. Data from Kelley et al. (2003).

obscured by the presence of multivariate outliers and non-
normal variable distributions (Reimann et al., 2002). Such
procedures generally require substantial preprocessing of data
prior to modeling and the recognition that geochemical vari-
ables display distributions that are complex and difficult to
transform (Pison et al., 2003; Reimann and Filzmoser, 2000).
Neural networks and the derivative self-organizing maps are an
alternative approach to revealing complex relationships within
multivariate datasets and identifying anomalies, as they are less
dependent on the characteristics of the input data than con-
ventional methods (Clare and Cohen, 2002; Kohonen, 1995).
Example: Geochemical patterns in regolith over the Chimborazo
deposit, Chile.
An example of signal detection, based on new models for
geochemical dispersion, is drawn from a regolith survey over
the Chimborazo deposit, Chile, where mineralization is
646 Exploration Geochemistry
covered by a thick gravel unit (Kelley et al., 2003). There is a
broad zone of elevated, but highly variable, Cu values across
mineralization (Figure 36). Despite the existence of a few
elevated As values over mineralization, the application of a
seven-point moving average across the profile indicates that
there has been no addition of As to the gravels above
mineralization, suggesting that the As content of the soils was
probably inherited with the gravel itself. Conversely, a seven-
point moving variance for the As data displays significant
increase in variance over mineralization. Hence, the target
geochemical signal for As is a change in spatial variance in
the gravels rather than addition or depletion of that element.
Acknowledgments
The authors are grateful to L.G. Closs, K.G. McQueen, and
N.F. Rutherford for their criticisms of the manuscript and the
numerous discussions about exploration geochemistry over
many years. The authors also thank their coworkers who have
contributed their ideas to previous reviews of exploration geo-
chemistry from which this manuscript has drawn, including
D.L. Kelley, R.R. Anand, W.B. Coker, and S.G. Gatehouse.
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