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Finding deeply buried deposits using


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Article in Geochemistry Exploration Environment Analysis February 2004


DOI: 10.1144/1467-7873/03-019

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Finding deeply buried deposits using geochemistry
Eion M. Cameron1, Stewart M. Hamilton2, Matthew I. Leybourne3, Gwendy E.M. Hall4
& M. Beth McClenaghan4
1
Eion Cameron Geochemical Inc., 865 Spruce Ridge Road, Carp, Ontario, K0A 1L0, Canada
2
Ontario Geological Survey, Sudbury, Ontario, P3E 6B5, Canada
3
Department of Geosciences, University of Texas at Dallas, Richardson, TX 75083-0688, USA
4
Geological Survey of Canada, 601 Booth Street, Ottawa, Ontario, K1A 0E8, Canada

ABSTRACT: It has become increasingly common for geologists to drill through


100 m or more of cover in search for buried mineral deposits. Geochemistry is one
tool applied to this search, using a variety of approaches, including selective leaching
of soils to extract the mobile component of elements, and the measurement of
inorganic and organic gases. This paper provides an overview of some of the work
carried out by the project Deep-Penetrating Geochemistry, sponsored by the
Canadian Mining Industry Research Organization (CAMIRO), and supported by
26 Canadian and international companies and by the Ontario Geological Survey and
the Canadian Geological Survey. The objective was to provide the mining industry
with information relating to processes that may form anomalies at surface over
buried deposits and to provide comparative data on methods used to detect these
anomalies.
Phase I of the project considered the theoretical and experimental framework for
the movement of material from deeply buried deposits to the surface; much of this
information has come from research on the containment of buried nuclear waste. In
arid or semi-arid terrain, with a thick vadose zone, advective transport, which is the
mass transfer of groundwater or air along with their dissolved or gaseous
constituents, is the only known viable means of moving elements to the surface;
diusion of ions in water or gases in air is orders of magnitude slower. Examples of
advective transport are pumping of mineralized groundwater to the surface during
seismic activity and the extraction of air plus gas by barometric pumping. Both
mechanisms require fractured rock and the interpretation of the derived anomalies
requires consideration of neotectonic structures. In wetter climates, where water lies
close to the surface, a variety of mechanisms have been proposed for creating
anomalies at the surface. Diusion-based models again suer from slow rates of
migration. Electrochemical models show a cathodic zone at the top of a buried
sulphide conductor. Cations are attracted to the cathode, rather than to the surface,
yet metals that most commonly migrate as cations are found to form anomalies at the
surface.
Phase II of the CAMIRO study involved field studies at ten test sites. The test sites
included buried porphyry deposits in northern Chile, a goldcopper deposit in the
Carlin district of Nevada, and volcanogenic massive sulphide bodies covered by
glacial sediments in the Abitibi greenstone belt of Ontario. In all cases anomalies
were found in soils above buried mineralization. It is suggested that anomaly
formation is an episodic and cyclic process, in which batches of metal in
water-soluble form are introduced and the metal is then progressively incorporated
with time into the secondary minerals of soil. Selective leaches have been developed
to dissolve specific phases in the soil to detect these anomalies. We have compared
the results for five selective leaches that are available from commercial laboratories:
deionized water, ammonium acetate, hydroxylamine hydrochloride, Enzyme Leach
and Mobile Metal Ion (MMI) plus one non-selective decomposition, aqua regia. In
addition, the Institute of Geophysical and Geochemical Exploration laboratory in
China has supplied data for four sequential selective leaches: water-extractable,
adsorbed, organic-bound and iron- and manganese-bound. The weakest leaches
dissolve mainly the most recently introduced metals that remain in water-soluble
Geochemistry: Exploration, Environment, Analysis, Vol. 4 2004, pp. 732 1467-7873/04/$15.00 ! 2004 AEG/Geological Society of London
8 E.M. Cameron et al.

form. Other leaches dissolve specific secondary minerals, such as carbonates, or iron
and manganese oxides, which contain the introduced metals. The usefulness of
leaches that dissolve secondary minerals depends on the ratio of introduced
(exogenic) metal that the minerals contain relative to that of endogenic origin derived
from the primary minerals of soils. Our results indicate that this ratio is variable from
site to site, so that there is no universal best leach for dissolving secondary minerals
in exploration surveys. For the test sites in Chile and Nevada, anomalies may have
formed incrementally over a period of a million years or more, which permitted
metals of exogenic origin to become incorporated into many secondary minerals. For
these sites, some anomalies can be detected by aqua regia, although the
anomaly/background contrast is less than for selective leaches. For the test sites in
Ontario, only a few thousand years have elapsed since glacial sediments were
deposited to conceal mineralization. Over this short period, metal of exogenic origin
has been incorporated into only the most labile of secondary minerals and it is the
leaches that dissolve these labile minerals that can successfully identify anomalies. At
the two sites where the most detailed studies have been carried out, the Spence
deposit in Chile and Cross Lake near Timmins, we have found that the optimum
sampling depth in soils is critical to detecting anomalies.
KEYWORDS: exploration, geochemistry, buried deposits, selective leaches, Chile, Nevada, Ontario

INTRODUCTION and government laboratories, has been limited by the available


funding. In contrast, over the past two decades, tens or possibly
The most frequently used geochemical method to identify hundreds of millions of dollars have been spent examining
buried mineral deposits is selective leaching of soil samples. processes that might cause dispersion of toxic materials from
These leaches remove only a fraction of the metal that might be buried nuclear waste. These processes are entirely analogous to
dissolved by aqua regia or by total dissolution, in the expec- those that might be involved in the dispersion of metals from
tation that this fraction represents a more readily dissolved buried mineral deposits. Moreover, a substantial portion of the
mobile phase, perhaps derived from an ore deposit. Leaches nuclear studies in the United States have been carried out in the
include the proprietary reagents, Enzyme Leach and Mobile arid terrain of the Southwest, similar to regions where
Metal Ion (MMI), and others that have been developed, companies are targeting buried deposits.
principally by soil scientists, to dissolve specific secondary The results of the Phase I scoping study encouraged a
minerals in soils, such as carbonates, or Fe and Mn oxides. The full-scale study to test methods and better understand pro-
leach solutions are most frequently analysed by inductively cesses. This was launched in 1999 as Deep-Penetrating Geo-
coupled plasma mass spectrometry (ICP-MS). This technique chemistry, Phase II. The project was again sponsored by
has shown progressive evolution, so that detection limits of rare CAMIRO and supported by 26 Canadian and international
elements have been lowered to levels thought unobtainable a companies. Test sites were selected in three regions, where
few years ago. This has had the eect of increasing the number companies are actively exploring for deeply buried deposits: the
of elements that can be measured with precision; now 50 or Abitibi greenstone belt of Ontario, where thick glacial sedi-
more are being reported. This benefit also presents a challenge. ments cover prospective rocks; the Carlin belt of Nevada,
With 50 elements at hand and the many ratios that may be where the most productive cluster of Au deposits in North
derived from these primary data, it is not too dicult to find an America has prospective areas of basement covered by the
anomaly over every known deeply buried deposit. The ease Carlin Formation; and thirdly, northern Chile, where basement
with which data may be obtained has led to the widespread rocks containing porphyry mineralization are covered by thick
application of selective leaches, with some successes, but many piedmont gravels. We looked at ten sites. In this account we will
dry holes and a poor understanding of the processes that might discuss five: (a) the Spence deposit, Chile, where 400 Mt of 1%
be involved in the creation of real or false anomalies. Cu is covered by piedmont gravel; (b) the Gaby Sur deposit,
This uncertainty caused a number of companies to propose Chile, where 400 Mt of 0.54% Cu is also covered by piedmont
a scoping study to the Canadian Mining Industry Research gravels; (c) the Mansa Mina deposit, where piedmont gravels
Organization (CAMIRO) to see how they might better under- conceal 325 Mt of 1% Cu; (d) the Mike deposit, Nevada, where
stand the processes that have caused anomalies to form above 240 m of Carlin Formation conceals a coppergold deposit; and
deeply buried deposits. This scoping study, Phase I of this (e) the Cross Lake prospect near Timmins where Zn-rich VMS
study, was carried out by Cameron over a six-month period mineralization of Archean age is covered by 30 to 50 m of
from October 1997. It was generously supported by 28 glaciolacustrine clay and sand.
companies, both Canadian and international. Several of these For the Phase II studies Stew Hamilton of the Ontario
companies provided data from their own orientation studies Geological Survey (OGS) assumed the major role of working
over known deposits. on the Abitibi sites and came with substantial funding from that
During the development of selective leach geochemistry, organization that permitted drilling of the overburden. Beth
ideas have emerged about processes for the dispersion of McClenaghan of the Geological Survey of Canada provided
elements from buried targets, the most prominent being elec- expertise as a Quaternary geologist. Before the study com-
trochemical dispersion. Research on dispersion mechanisms by menced, it was apparent that groundwater might have played an
the exploration community, including researchers in universities important role in the formation of surface anomalies in
Finding deeply buried deposits using geochemistry 9

northern Chile. Matthew Leybourne of the University of Texas


at Dallas led the studies of groundwater geochemistry. Mary
Doherty of BHP Minerals and International Geochemical
Consultants participated in the studies at Mike. The project
involved comparing dierent leaches, and Gwendy Hall of the
Geological Survey of Canada took responsibility for the
analytical programme. We were fortunate to get the support of
all major commercial analysts in Canada, who provided analyses
gratis and also communicated much of their knowledge: John
Gravel of Acme Laboratories, Eric Homan of Actlabs, Brenda
Caughlin and Pat Highsmith of ALS-Chemex, Claude Massie of
Bondar-Clegg, Robert Ellis of Gedex and Hugh De Souza of
XRAL. Moreover, Xie Xuejing of the Institute of Geophysical
and Geochemical Exploration (IGGE) in China provided
analyses by methods typically used in that country. Thus, for Fig. 1. Chloride content and estimates of moisture flux for profiles
many of the samples there are nine sets of analyses to compare. of unsaturated soils, Hueco Bolson, Texas. Scanlon (1991).
Starting in 1999, 38 reports on the Phase II project were
released to sponsors on topics as dierent as biogeochemistry, of recharge to the water table about 13,000 to 15,000 years ago,
hydrology and Pb isotopes at the Abitibi sites, stable isotopes in when the climate began to shift from cooler and wetter to
groundwater and soils from Chile and soil gas tests in Nevada. the current arid conditions. When precipitation is greater,
This article touches on only a few of these topics and includes profiles move slowly downwards as water and Cl are added
only information for which a two-year confidentiality limit has incrementally at the top, thus providing a view of changing
expired. moisture fluxes with time. The 15 m profile shown is esti-
mated to represent 30,000 years. Below the bulge, the
decreasing Cl contents indicate an increasing moisture flux
PROCESSES FOR THE VERTICAL MIGRATION OF prior to 15,000 years.
ELEMENTS Mathematical methods of relating Cl concentration to
moisture flux are given in Scanlon (1991). An advection
Migration of dissolved solids in water diusion equation can be fitted to the data to evaluate the
Solids dissolved in water may migrate within the water mass relative importance of these two factors on the mobility of Cl.
diusion or may migrate as part of a moving water mass The very large concentration gradients represented by the bulge
advection. Diusion, the first of these to be discussed, may provide a driving force for diusion, which will tend to smooth
occur as a result of a chemical or electrical gradients. the bulge. Above the peak in the bulge, the upward diusive
fluxes of chloride are 10"3 to 10"4 mm a"1. Below the peak,
Diusion through the vadose zone. For all but the wettest of areas, the downward fluxes are 10"3 to 10"5 mm a"1. The down-
vertical transport of elements from a buried deposit to the ward advective flux is 10"1 to 10"2 mm a"1, or two to three
surface must include passage through the vadose or undersatu- orders of magnitude greater than the diusive flux.
rated zone. Except for hyper-arid climates, the vadose zone is The moisture content has a direct eect on the migration of
not dry. There is a film of water around mineral grains of the dissolved material by diusion. As the ground becomes drier,
rock. This film of water is in downward motion and serves to liquid flow paths become more tortuous and the degree of
recharge to groundwater the water from precipitation remaining liquid interconnection decreases. Some flow paths may dead
after evaporation and run-o. The rate at which this water film end. Whereas water molecules may move in the vapour phase
moves can be estimated by measuring depth profiles of across air-filled pores, involatile solute molecules must follow
elements and isotopes in the water film extracted from drill tortuous connected liquid pathways. There will be flow into
core. Since it is a conservative element, Cl is widely used. Rain dead-end paths, since water continues to move in the vapour
contains Cl, the content of which, per volume of precipitation, phase. Non-volatile dissolved molecules can only escape from
is relatively constant over time for a given area. With increased dead-end paths by diusion back out against the flow direction.
aridity and therefore evapotranspiration, the Cl content of soil Thus, involatile dissolved molecules, such as Cl, move more
water increases and the downward flux of moisture recharging slowly than water. This has been demonstrated by isotope
to the groundwater decreases. studies, including 36Cl and 3H, released during atomic bomb
Figure 1 shows data from core of the top of the unsaturated tests. 36Cl was generated during sub-sea tests and fallout peaked
zone from the Hueco Bolson region, near El Paso, Texas. This in 195556. 3H was generated during atmospheric tests and
alluvial plain slopes 1 to 1.5% to the Rio Grande. Creosote and peaked later, in 196465. Once incorporated into soil moisture,
mesquite are common and root to 1 to 5 m depths. Mean these isotopes behave dierently. 36Cl is non-volatile and is
annual precipitation is 28 cm. The unsaturated zone comprises restricted to liquid phase flow, whereas tritiated water, like
0 to 15 m of silty to gravel loam, underlain by 140 m of clay normal water, can move in either liquid or vapour phases.
with interbedded sand and silt. A discontinuous layer of caliche Scanlon (1992) measured the penetration of 36Cl and 3H into
occurs at 1 to 2 m. Chloride was measured after adding the soils of the same region, Hueco Bolson, referred to above.
deionized water to dried core samples. The content is low from The 36Cl/Cl ratio reaches a maximum at 0.5 m depth (Fig. 2).
the surface to 0.3 m, the result of downward leaching by rain. Although 3H peak fallout was eight years later than 36Cl, tritium
Below this, Cl increases as a result of evapotranspiration, penetrated deeper, below 1 m, indicating that faster migration
forming a bulge with maximum concentrations at depths of 1.3 is possible in the vapour phase compared to dissolved
to 4.6 m for dierent cores. This bulge occurs throughout the components.
southwestern United States, just below the root zone (Phillips
1994). It corresponds to a minimum in the moisture flux, i.e. a Electrochemical dispersion. Electrochemical cells are generated
maximum in evapotranspiration, which represents a cessation around most sulphide bodies as a result of their oxidation and
10 E.M. Cameron et al.

Fig. 3. Supergene alteration caused by electrochemical oxidation of


pyrrhotitepentlandite ore in arid terrain. From Blain & Brotherton
(1975); Thornber (1975).

Fig. 2. Vertical profiles of 3H and 36Cl/Cl for unsaturated soils,


Hueco Bolson, Texas. Scanlon (1992).

are often detectable by negative self-potential (SP) anomalies


above the bodies. A sulphide body can be considered a
conductor immersed in an electrolyte, groundwater. Redox
dierences exist between the more oxidized upper (cathodic)
portion of the body and the more reduced deeper (anodic) part.
Anodic corrosion takes place at depth between sulphide min-
erals and the electrolyte, releasing electrons: MeS # M2+(aq) +
S + 2e". Electrons travel, usually upwards, through the
conductive sulphide body to locations where oxygen or other
oxidants are available and take part in its cathodic reduction: O2 Fig. 4. Conceptual model by for the electrochemically induced
dispersion in arid terrain (Elura deposit, Australia). For Elura, the
+ 4H+ + 4e" # 2H2O. Because of the electrical potential sulphide has been completely oxidized to a depth of 98 m and the
established between the cathodic and anodic sites, there is water table lies between 80 and 115 m. Diagram simplified from
current flow, carried by ions in the groundwater. Cations Govett et al. (1984).
migrate to the cathode and anions to the anode. Cathodic
reactions are usually shallow, close to the supply of oxidants
near the water table. Water is required as a source of dissolved results were obtained by Govett (1975) for a variety of
oxidants and to permit the migration of dissolved cations and locations, with unambiguous conductivity anomalies found over
anions, which carry the current. One well-described cell is that deposits with shallow cover.
produced by the massive nickel sulphide deposits at Kambalda, Smee (1983); Govett et al. (1984) developed similar models
Western Australia (Fig. 3). for the formation of twin or rabbit ear anomalies at the
Much of the pioneer work in exploration geochemistry on surface above an oxidizing sulphide deposit. Whereas
electrochemical cells involved sulphide bodies that reach close Govetts model was for transfer through the vadose zone in arid
to the surface. Air and infiltrating rainwater, saturated in terrain, Smees was for migration through saturated clay. In
oxygen, bathe the cathodic zone. Bolviken & Logn (1974) Govett et al.s model, cations following the current path
described an electrochemical cell formed by the Joma deposit, accumulate on either side of the sulphide body in a zone of high
Norway, which is covered by 0.5 to 1.2 m of glacial sediments. current density near the base of the conductive weathered zone
There is a well-developed SP anomaly detectable at surface. (Fig. 4), which is near to the water table. From these zones of
Samples of till, taken as close as possible to bedrock, showed high concentration, cations move to the surface by chemical
elevated concentrations of metals over the mineralization and diusion. But, as described in an earlier section, chemical
display higher conductivity in watertill slurries. Increased diusion within the water film coating grains in the vadose zone
conductivity supports the contention that free mobile ions is much slower than the downward advective flow of the water
should be more abundant near the upper cathodic zone. Similar film.
Finding deeply buried deposits using geochemistry 11

water table there is ready access to O2, permitting oxidation of


the reduced material. This will produce a number of eects,
including a decrease in pH and the concomitant dissolution of
carbonate (Fig. 5). The reduced column, pH lows and dissolu-
tion of carbonate predicted by this model have been docu-
mented at the Cross Lake site discussed below and at other
locations in the Abitibi greenstone belt. And elements present
in the mineralization, such as Zn and Cd, show clear anomalies
in the soils above. There are also negative SP anomalies,
indicative of current movement in the conductor. There are
considerable technical diculties in fully evaluating the pro-
cesses that occur within the reduced column. To create the
features seen at the surface at Cross Lake, where 30 m or more
of clay lie above the sulphide lens, and within a period of 8,000
years since the clays were deposited, requires rates of migration
well beyond that of chemical diusion.

Advective flow. Water and its dissolved contents typically flow


Fig. 5. Conceptual model from Hamilton (1999) showing the eects down-gradient, not upwards. However, there are some
of the dispersion of a reduced column of metal and other exceptions. One of these is the eusion of groundwater at the
constituents upwards through clay overburden from sulphide min- surface during earthquakes. In the Phase I scoping report by
eralization exposed at the subcrop. The reduced material reacts with Cameron (1998), this mechanism was given less than a page,
oxygen at and above the water table to form acid, which dissolves because it was considered unlikely to produce significant surface
and redistributes carbonate. anomalies. However, in the subsequent field programme in
Chile this appeared as an important process for anomaly
Smees model is for the Abitibi greenstone belt, where thick, formation.
>30 m, generally saturated, glaciolacustrine clays often cover Earthquake-induced surface flooding by groundwater has
mineralization. Cations that concentrate at the base of the clays long been recognized. Sibson (1981), p. 593) described ground-
diuse upward. Diusion coecients of 1x10"10 and 1x10"11 water movements along fault lines after earthquakes: In arid
m2 s"1 are typical ranges for non-reactive chemical species in terrain particularly, there are reports of changes in well water
clay. A diusion front representing only one percent of the level, spring flow and occasional dramatic eusions of ground-
original concentration would reach 10 m out from source after water immediately following moderate to large shallow earth-
10,000 years. This is for one-dimensional diusion, whereas quakes. Surface flows occurred in a desert area of Iran during
dispersion from an orebody would be radial, resulting in lower earthquakes in 1903 and 1923 (Tchalenko 1973). During the
concentrations at a given distance from the deposit. Clays may magnitude 7.3 Salmas earthquake of 1930 in NW Iran, water
act as a semi-permeable membrane, resisting the diusion of was expelled along the main fault trace and a broad area of
ions (Schwartz 1974) or clay mineral surfaces may adsorb metal alluvial plain on the downthrow side became fissured and
ions. The limited nature eect of either advective or diusive waterlogged (Tchalenko & Berberian 1974). Nur (1974)
flow in thick glaciolacustrine clays since their time of deposition noted outpourings of warm groundwater accompanying the
is illustrated by the empirical data of Remenda et al. (1994). They Matsuchiro earthquake in Japan. Following the Hebgen Lake
found that at depths of 20 to 30 m in clay from various sites in earthquake of Montana in 1959, three rivers increased in flow
the southern Canadian Shield, interstitial waters retained !18O by c. 50%, the increases continuing for several weeks through
compositions of "24 to "25 characteristic of surface dry weather (Muir-Wood 1994). The Kern County, California,
waters at the time of deposition. These waters have been static, magnitude 7.5 earthquake of July 1952 was followed by two
showing no evidence of equilibration with modern waters in the months of drought. There were outpourings of groundwater in
area of "13 to "14. Thus, neither advection or diusion the vicinity of faults, and increases in spring flow and well water
has been eective in moving these waters over the last c. 10 ka. level, which continued for two months (Briggs & Troxell 1955).
Although electrochemical processes are an important means for Sibson et al. (1975) used the term seismic pumping to explain
releasing ions from a buried sulphide body, there is diculty in this process. Pre-seismic extension produces fractures in the
explaining how the ions so released travel to the surface. brittle upper crust that provide pathways for groundwater
A dierent model was proposed by Hamilton (1998, 1999, migration and storage. During earthquakes, stress fields become
2000) for saturated overburden in glaciated terrain where the compressional, closing fractures and forcing groundwater to the
sulphide subcrop is covered by tens of metres of glacial surface along faults. Given the low permeability of basement
sediments. This model (Fig. 5) invokes transport along redox rocks, groundwater is slow to migrate to faults, resulting in
gradients. Consumption of oxidants at the sulphide/sediment continued eusion of water for weeks following an earthquake.
interface creates a reduced environment. Continued oxidation Groundwaters expelled from depth are typically old and saline,
can only occur if reduced species are removed. Redox dier- but may mix near-surface with less saline waters.
ences between the top of the body and the water table near the There are other mechanisms for the advective transfer of
surface, where oxygen is in contact with groundwater, produce groundwater and solutes to the surface. One that was applied
a vertical electrochemical gradient. Reduced species, such as early in the history of exploration geochemistry is advective
HS" and Fe2+, migrate upward along this gradient and transfer by deeply rooted plants. Analysis of the plant material
reactions between oxidized species moving in the opposite provides information on the composition of deep groundwater.
direction dissipate charge away from the sulphide. As the In some arid areas, plants have been found to root as deep as
limited number of oxidizing agents between the top of the body 100 m (Cannon & Starrett 1958). Also, capillarity can draw
and the water table are consumed, a reduced column is groundwater from the water table to the surface, where it
postulated to form between the body and the water table. At the evaporates. However, the water table must be relatively close to
12 E.M. Cameron et al.

was detected at sites OS1, OS2 and OS3. 3He was first detected
at the surface at OS6, 375 days after detonation.
These empirical observations are entirely contrary to migra-
tion by gaseous diusion. 3He has a much higher diusivity than
SF6 and, if diusion was the dominant mechanism, should
reach the surface long before the other gas. The diusivity of
SF6 is such that it would require 10 s to 100 s of years to reach
the surface, yet it has happened in days. Why? The reason is that
gaseous diusion is overridden by a much faster mechanism,
barometric pumping. The description of barometric pumping
given here is largely derived from Nilson et al. (1991), work
carried out at the NTS.
Barometric pumping refers to the process where cycles of
high and low barometric pressure first force air into the earth
and then withdraw a mixture of the air plus gases that were in
rock. For all practical purposes, barometric pumping applies
Fig. 6. Rainier Mesa, Nevada, showing the location of a cavity for a only to fractured rock. For reasons discussed below, barometric
1kt explosion. Bottles of SF6 gas and 3He gas were set close to the pumping is not a significant process for non-indurated, unfrac-
explosion. SF6 first reached the surface at site OS6 50 days after the tured material, even if permeable. When the permeability of
detonation during a barometric low. 3He arrived only after 325 days. NTS alluvium is measured on small samples in the laboratory or
From Carrigan et al. (1996). large volumes are measured in situ in the field by borehole
injection, results are similar, in the range 1 to 15 darcy (D).
the surface, since the height over which the water can be drawn When the permeability of NTS volcanic rock is measured on
is dependent on the parameter known to soil scientists as soil core samples in the laboratory and again by borehole injection,
suction. Soil suction depends on the nature of the soil and the results are very dierent, only 10"6 to 10"2 D on core, but 1
degree of dryness. Clay soils exert greater suction than sand or to 15 D for borehole injection, the same as for the alluvium.
silt and dry soils more than damp. Fontes et al. (1986) describe The higher permeability of the bulk rocks is because fractures,
a site in the Sahara Desert where capillarity draws water to the not present in the small laboratory core samples, control the
surface from a depth of 10 m. They suggest that 20 m may be permeability.
a limiting depth for this process. High barometric pressure forces air down fractures and into
pore space in the rock around the fractures. Gases within the
rock, such as CO2 or hydrocarbons, mix with air by molecular
Migration of gases and the eects diusion. When the barometric pressure drops, air in the
Lovell et al. (1983); McCarthy et al. (1986) and others have porous rock, now containing the gases, returns to the fracture
shown that gases such as carbon dioxide and methane are more and, after several cycles of high and low pressure, reaches the
abundant in soils above some deposits, whereas oxygen is surface. Pumping occurs because the volume of air entering
depleted. Clark et al. (1997) have argued for the migration of rock porosity is much greater than the volume of air present in
halogens and volatile metal compounds to the surface. Chinese the fractures. The rock porosity provides the breathing volume
geochemists (e.g. Xie et al. 1997) have suggested that a variety of that permits large vertical movements during high pressure
elements, Au, As and Sb, are carried to the surface in mobile inhalation and low pressure exhalation. By contrast, in
form by gases, including very fine particulates, in the sub- non-fractured permeable media, such as alluvium, air move-
micrometre to nanometre range. Hydrocarbons are currently ments are piston-like and nearly reversible, so that there is little
being measured in soils. The SGH method of Actlabs Ltd upward transport of a gas of deep origin. For a fractured
(Ancaster, ON, Canada) desorbs and measures hydrocarbons in permeable medium, barometric transport can be several orders
the C5 to C17 range from B-horizon soils. A similar method, of magnitude greater than molecular diusion, whereas for
soil desorption pyrolysis (SDP, St. Lucia, Queensland, unfractured soil and alluvium, molecular diusion is more
Australia), has also been developed for hydrocarbon gases in important.
soils. Similar to dissolved solids in water, gases may migrate by Using data from NTS volcanic rock, simulations were carried
diusion through air or water, or advectively, as a result of the out on the removal by barometric pumping of a deep gas. With
movement of a mass of air or water containing the gases. For the condition of fresh air from the surface to 200 m, then air
gases, as for dissolved solids in water, advective flow is a far plus radioactive gas from 200 m to the water table at 500 m,
more rapid transport mechanism than diusion. 10% of the contaminated gas was removed in one year. In terms
of geological processes this is rapid. The overall eciency of
Barometric pumping. Carrigan et al. (1996) carried out a simulated deep gas transport to the surface is critically dependent on the
underground nuclear test. A charge of 1.3 $ 106 kg of chemical spacing of fractures. For closely spaced fractures, say only a few
explosives, equivalent to a 1 kt nuclear charge, was detonated at centimetres or less, each fracture has only a small breathing
a depth of 400 m in bedded tu at Rainier Mesa in the Nevada volume of porous rock around it. The transport eciency
Test Site (NTS) (Fig. 6). Two bottles of gas were placed near to increases with increasing fracture spacing up to a few metres.
the charge. One contained 3He and the other SF6. The amounts But after about 10 m spacing there is no incremental benefit
of gas involved were not large, for 3He, 1.3 m3 and for SF6, because the air can only penetrate a few metres in the half
8 m3. The detonation chamber was close to a fault. After the period of about 100 hours that is usual between high and low
explosion, sampling sites were established at the surface to barometric phases. Maximum transport eciencies are reached
detect these gases. The first gas to be detected was SF6 along for spacing in the range 2 to 10 m. Although it may initially
the fault at site OS6, 50 days after detonation, during a strong appear counterintuitive, transport eciencies are decreased
barometric depression. The fault along where OS6 is sited is not with increasing molecular diusivities of gases. This is because
the one that runs close to the detonation cavity. Thereafter, SF6 a gas with high molecular diusivity can more readily diuse out
Finding deeply buried deposits using geochemistry 13

greatest enrichment with a factor of c. 2000. Fractionation is


increased with increasing length of the water column through
which the bubbles pass. Metals are most strongly enriched in
sub-micrometre aerosols (Arimoto et al. 1990). Aerosols in the
size range 0.1 to 10 m have a residence time in the lower
atmosphere of about a week. The small size of these particles
favours transfers from the solid to vapour phase and reactions
between the gases and solids, which may form volatile com-
pounds
What are the possible relationships between oceanic aerosols
and ore deposits? Gases may perhaps be generated during the
oxidation of sulphides or gases from deeper sources, e.g. the
mantle, and may rise up faults along which deposits lie. Some
Fig. 7. Heavy metal enrichments in the marine atmosphere. Enrich-
ment is measured relative to crustal abundance normalized to Al. samples of groundwater taken from the Spence copper
Data from Rahn (1976) and for Hg from Crozat et al. (1973). porphyry deposit, Chile, were found to be saturated with CO2.
The degassed CO2 can rise as bubbles through groundwater,
scrubbing metals from the water en route. Mineralized ground-
of the upward-moving air/gas mixture in the fractures into waters have concentrations of metals orders of magnitude
porous wall rock. This explains why in the bomb-simulation greater than sea water and bubbles are likely to scrub a greater
experiments SF6 arrived at the surface more speedily than 3H, depth of water than the one or two meters typical of wave-
which has a higher molecular diusivity. Diusion of hydro- generated bubbles. Barometric pumping may serve to extract
carbons out of the upwardly rising air/gas mixture into the sub-micrometre aerosols from the water table, but this has not
surrounding wall rock may explain a reduced column of rock been demonstrated. Even where aerosol generation is minimal,
above a leaking hydrocarbon reservoir. bubbles, with a high concentration of metals in the boundary
layer, may deliver metals to the water table. This may be of
Seasonal exhaustion of air and gas from the vadose zone. Yucca significance in wet areas, where the water table is close to the
Mountain, Nevada, rises 250 m above Solitario Canyon. In surface.
winter, air within the mountain is warm. This warm air rises and The Osborne deposit, in northern Queensland is a copper
is replaced by cold, denser air entering at the base of the scarp. gold replacement deposit in lower Proterozoic metamorphic
Air exhausts continuously, at a relatively high velocity, typically rocks, covered by 30 to 60 m of fractured sedimentary rock of
3 m s"1, from wells drilled near the crest of the mountain Mesozoic age. Placer Australia Pty sponsored a series of
(Weeks 1987). In summer, the wells alternately intake and geochemical tests over the deposit prior to mining, including
exhaust air several times a day, but at lower velocity. A farmer pSirogas collectors (Rutherford et al. in press). A plastic
in Idaho drilled a 30 m dry well into the Snake River basalts, collector containing a polystyrene film was buried in the soil at
near the Snake River Gorge. He built a greenhouse over the a depth of 50 cm. A hole in the base of the container allowed
well, with the air exhausting from the well maintaining plant soil air to circulate over the polystyrene film. After 30 to
growth through the winter. This process for the advective 60 days, the collectors were recovered and the surface of
movement of air plus gas has been described by Rose & Gow the films analysed by Particle Induced X-ray Emission
(1995). Spectrometry (PIXE) for a variety of trace metals. The surfaces
of the films were also examined by Scanning Electron
Migration as bubbles and bubble-generated aerosols. Whereas baro- Microscopy (SEM). These scans show circular areas of precipi-
metric pumping provides a mechanism for the advective tate, 20 to 30 m in diameter, which they attribute to the
transfer of gases to the surface in arid terrains with a thick, impingement, then evaporation, of water or aerosol droplets.
fractured vadose zone, bubbles provide a means for advective Most of the geochemical data from Osborne are erratic between
movement through the saturated zone. Kristiansson & adjacent sites (spikey), perhaps reflecting transport up
Malmqvist (1982) found that the radon migrated to the surface fractures, with the pSirogas results showing this strongly,
much faster than can be accounted for by diusion in ground- including the strongly anomalous results for Cu (Fig. 8).
water. They suggested that radon was included in microscopic
bubbles composed of nitrogen, argon, oxygen and methane. Mineralogical change in soils by gases. The passage of gas from a deep
Bubbles and bubble-generated aerosols may be involved in source through soils may cause changes in the soils com-
the upward transport of the dissolved constituents of ground- position or mineralogy. A possible, if extreme, example is
water. The clue for this is metal-rich aerosols over the oceans. shown by analyses of soils above underground nuclear test
Some elements are greatly enriched in the marine atmosphere explosions in Nevada (Hall et al. 1997). In these tests, deton-
relative to their crustal abundance (Fig. 7). When waves break, ations were at the bottom of a vertical shaft that had been
air is trapped in seawater, which rises as bubbles. Surface-active back-filled and cemented. For the described sites, explosions
substances are attracted to the bubblewater interface. These took place at depths of 293 to 350 m, well above the water
include bacteria, colloids, soluble organic molecules and dis- table, at 450 to 530 m. Data shown on Figure 9 are from soil
solved heavy metals (Piotrowicz et al. 1979a; Piotrowicz et al. samples taken across the Ville test site, where the explosion
1979b). As bubbles rise they scrub the water of these caused a surface slump crater 120 m in diameter and 17 m deep.
substances. At the surface of the ocean there is a surface Analyses after a hydroxylamine extraction show a strong
microlayer, enriched in the same surface-active materials. When anomaly for I, extending for 300 m on either side of ground
a bubble bursts, aerosols are formed from the bubble boundary zero. Iodine is an element that forms a variety of volatile
layer and from the surface microlayer. Experimental studies of compounds. Arsenic shows a weaker anomaly and also can
aerosol generation show strong fractionation of elements. form volatile compounds. The presence of anomalies for
Piotrowicz et al. (1979) found that Fe was not enriched, whereas volatile elements suggests the passage of these plus possible
Cu, Cd and Zn were enriched by a factor of 200. Lead had the carrier gases through the soil. But also note the strong depletion
14 E.M. Cameron et al.

Fig. 8. Cu in soil air over Osborne


deposit, Line 21737N, as measured by
CSIROGAS collectors. Deposit lies
below 11200E to 11600E. Modified
from Rutherford et al. (in press).

in the amount of Fe extracted. Analyses for the total contents including a mineral deposit, are termed the exogenic phase. The
of Fe and other elements showed a flat pattern: there has been exogenic phase is initially added to the soil in water-soluble
no change in the bulk composition of the soils above the form; as a result of soil-forming processes, this phase is
detonation site; only the small fraction of selected elements that progressively incorporated into secondary minerals (Fig. 11).
can be dissolved by a selective leach. The depletion in Fe shown Each secondary mineral contains elements of both endogenic
by the selective extraction may be the result of gas changing the and exogenic origin. The relative amounts of these phases vary
mineralogical state of the Fe oxide minerals, such that Fe was between minerals and, for a given mineral, from place to place.
less easily dissolved by the hydroxylamine leach. The possibility Given that the exogenic phase must first enter a soil in a
that the observed changes may be the result of contamination water-soluble form, one approach is to use a weak leach that
during drilling have been discounted by more recent unpub- does not attack any minerals, but dissolves water-soluble salts
lished work where the nuclear device was placed using a and elements loosely adsorbed to mineral surfaces. Pure water,
horizontal adit. Soils over the Ruby Star copper skarn deposit, i.e. deionized water, is the most simple leach for this purpose,
Arizona (Fig. 10) are also depleted in Fe, when measured by a but suers from poor analytical reproducibility. An alternative is
selective leach. Until more detailed studies are carried out, the the Enzyme Leach. In our experience, this leach dissolves little
causes for these depletions must remain speculative.

Measurement of elements and gases in soils


Selective leaches. Most applications of geochemistry to exploration
for buried deposits involve the analysis of soils by selective
leaches (Hall, 1998). The term selective leach was first applied
by soil scientists to reagents that could dissolve particular
mineral phases, with minimal eect on other minerals. In
exploration geochemistry, selective leaches are used to dissolve
minerals that may include a high proportion of the mobile
phase of elements, including material derived from deposits.
Soil-forming processes convert primary minerals derived from
rocks into minerals stable at low temperature. The element
fraction that comes from primary minerals is here considered
the internal or endogenic phase. Elements from external sources,

Fig. 10. Iron and Cu by Enzyme Leach in soils over the Ruby Star
Fig. 9. Contents of Fe, I and As in soils collected along a traverse copper deposit, Arizona. Data are moving average of three sites.
crossing ground zero (0 m on horizontal scale) above the Ville atomic Deposit contains 100 Mt 1% Cu and consists of massive slump
bomb test, Nevada. Soils were extracted with hot hydroxylamine blocks enclosed within fanglomerate and covered by 40 to 300 m of
(HX Fe). From Hall et al. (1997). gravel. Data from Kelley (1995).
Finding deeply buried deposits using geochemistry 15

Fig. 11. Conceptual model showing the


distribution of exogenic and endogenic
phases between soil-forming minerals.

more than deionized water (Fig. 12), but the analytical repro- extracted or are reprecipitated or adsorbed as the pH increases.
ducibility is better. The other main proprietary leach, Mobile Thus analytical laboratories should measure and report the final
Metal Ion (MMI), comes in several forms, two of which are an pH of the leach solution. The ICP-MS is subject to spectral and
acidic MMI-A and a basic MMI-B. The MMI-A leach (targeting non-spectral interferences, which may aect the determination
Zn, Cu, Pb, Cd) dissolves more metal than the Enzyme Leach, of numerous elements, particularly those at low concentration
which indicates that it is dissolving secondary minerals. How- (Hall 1992). For example, mass 105Pd is commonly used to
ever, the formulations of the MMI solutions have not been measure Pd, but this is also the mass for the molecular band
105
published and, because major elements are not determined by (SrOH). Palladium is usually present in soils in the low ppb
the laboratories carrying out MMI analyses, it is not possible to range and its signal can be overwhelmed by SrOH formed in the
interpret which mineral phases are being dissolved. plasma during analysis of soils of moderate to high Sr content.
The second approach is to use a leach that dissolves one or Quality control on analyses is mandatory for surveys, using
more secondary minerals that contain a favourable ratio of hidden duplicates and standards, the latter being samples that
exogenic to endogenic material at a particular site. Ammonium have been analysed in previous surveys. Analytical duplicates
acetate at pH 5 dissolves carbonate minerals. For oxide are separate vials of the same prepared sample, given dierent
minerals, hydroxylamine hydrochloride is widely used. Cold numbers and placed at distant positions in the submitted
(room temperature) hydroxylamine in an acidic solution, pH c. analytical batch. Field duplicates are separate samples collected
1.5, (HX Mn) dissolves Mn oxides, whereas hot (60 oC) at the same site, but 2 to 5 m apart from each other. After
hydroxylamine in a more strongly acidic solution (HX Fe) analysis, the analytical and field duplicates are separated into
dissolves both Mn and Fe oxides. Because both hydroxylamine groups and the standard deviation, s, and relative standard
leach solutions are acidic, they will also dissolve carbonate, so deviation, RSD, are computed for each:
that the element phases extracted are the sum of those present
in carbonates and oxide minerals, plus, of course, that present s2 = ~!~xi1 " xi2!2!/2N
in water-soluble form. In general, the more acidic the leaches,
the less selective they become. For organic material, such as RSD = 100 s/X where the squares of the dierences between
humus, sodium pyrophosphate is the most commonly used the duplicate pairs are summed, then divided by 2N, N being
leach, although it tends to dissolve large amounts of elements of the number of pairs, to produce the variance estimate s2. The
endogenic origin, unrelated to mineralization. Aqua regia should mean of all duplicates, X, is then used to calculate RSD.
also be mentioned. This is not a selective leach, but dissolves In Figure 13 RSDs are shown for 29 elements as determined
most secondary minerals and partially extracts some silicates. by the Enzyme Leach. The RSDs were computed from ten pairs
Because it dissolves a high proportion of endogenic phases, the of analytical duplicates of B-horizon soils from the Abitibi test
anomaly to background contrast is generally low. However, it sites. The median RSD is also shown. The median RSD of the
provides useful information on the overall composition of the analytical duplicates for each leach provides a useful compari-
soils, which assists in the interpretation of the selective leach son of analytical precision between dierent leaches. In Table 1,
data. And it may give good results for mature anomalies, where median RSDs for five leaches have been compiled. In general,
elements of external origin are no longer being introduced. the stronger the leach, extracting more of each element, the
There are complexities involved in the use of selective lower is the RSD. This is because it is more dicult to
leaches, which require consideration during survey planning, consistently extract a small fraction of the element present than
analysis and interpretation. When significant amounts of car- a large fraction. The amounts of elements extracted by the
bonate are present in soils, this can partially neutralize leach dierent leaches, as shown in Figure 12, correlate with the
solutions that contain acid, so that their leaching capacity is RSDs given in Table 1. Other than deionized water, the RSDs
degraded. For example, 1215% CaCO3 in samples can increase obtained from the selective leaches are satisfactory. The vari-
the pH of a cold hydroxylamine (HX Mn) solution from c.1.5 to ance estimate, s2, for the field duplicates is the sum of the
5.5 and MMI-A from c. 2.5 to 6. Element contents that might analytical variance plus that due to sampling. Thus the RSDs for
be extracted in the absence of carbonate may not be fully field duplicates are higher than those for analytical duplicates
16 E.M. Cameron et al.

Fig. 13. Relative standard deviation (RSD) for ten pairs of analytical
duplicates of B-horizon soils from the Abitibi belt analysed by
Enzyme Leach.

every 10oC increase in temperature and is also influenced by soil


moisture and the content of organic matter (Amundson &
Davidson 1990). Carbon dioxide dissolves in water, forming
H2CO3, HCO3" and CO32". Thus the presence or absence of
moisture can substantially influence the concentration of this
gas. An alternative, that reduces temporal variations, is to
measure the integrated flux, such as is done with radon by
burying alpha track film in the soil for days or weeks or
adsorbing gaseous Hg on Au film. For metals in soil air, CSIRO
in Australia and BRGM in France place collectors in the ground
for c.100 days. In the BRGM method (Pauwels et al. 1999) the
metals are collected on activated carbon, whereas in the CSIRO
method (Rutherford et al. in press) solids and vapour impinge
on a thin plastic film. Organic gases are absorbed on clay
minerals. By desorbing these gases, then measuring their relative
abundance, clues may be obtained to buried deposits. This is the
basis of the SGH (Soil Gas Hydrocarbons) technique of Actlabs
and the SDP (Soil Desorption Pyrolysis) method of the
University of Queensland.

Fig. 12. Box-whisker plots showing the amounts of element


extracted by deionized water, Enzyme Leach, MMI-A, ammonium FIELD TRIALS
acetate at pH 5 (AA5), cold hydroxylamine (HX Mn) and aqua regia.
Top of the diagram, Cu in 63 samples of soil from a traverse across Study areas and methods
the Spence copper deposit. Bottom of diagram, Zn in 54 samples of Phase II of the CAMIRO Deep-Penetrating Geochemistry
B-horizon soils from two traverses across VMS mineralization at project was to carry out studies at test sites where known
Cross Lake, Ontario. mineralization is covered by 30 to 240 m of rock or consoli-
dated or unconsolidated overburden. Sites were chosen in the
Abitibi greenstone belt of Ontario, the Carlin district of
(Table 1). Only in the case of the deionized water leach is the Nevada, and the Atacama Desert of northern Chile. The
RSD for the analytical duplicates so high that it approaches the characteristics of these sites are summarized in Table 2 and the
RSD of the field duplicates. individual studies carried out at each site are listed in Tables 3
and 4. These three regions were chosen because of their
Measuring gases. Soil gases are commonly measured directly in the geological and climatic contrasts. The Atacama is the driest
field using instrumentation. This confers the advantage that large desert area of the world and is host to some of the
anomalies may be investigated immediately. The disadvantage is largest and lowest-cost Cu deposits. Carlin is the most produc-
that the instantaneous flux of gas so measured is subject to tive district for Au in North America and has a semi-arid
many environmental variables that may change the estimated climate. The Abitibi, a glaciated region with a boreal cool
concentration. In a study of radon activities from sites in humid climate, contains many major lode Au and volcanogenic
Pennsylvania, Rose et al. (1990) found that readings from depths massive sulphide (VMS) deposits.
below 70 cm varied by factors of 3 to 10 during the year for Work in Chile and Nevada was entirely funded by company
dierent sites. At shallower depths, seasonal variability is even sponsors through CAMIRO. Much of the work in Ontario was
greater. Temperature and moisture variations, rain, wind and funded by the Ontario Geological Survey (OGS). Reports on
barometric change may all aect the measured concentration. individual studies were provided to the company sponsors on
Carbon dioxide shows variation due to seasonal, sampling an ongoing basis starting in 1999. In November 2001, a
depth and environmental changes similar to that of radon. The CD-ROM containing 31 reports and seven database files was
flux of CO2 in soils increases by between 1.5 to 3 times for distributed. These results were reviewed at a meeting held in
Finding deeply buried deposits using geochemistry 17

Table 1. Relative Standard Deviations (RSD) for ten pairs of analytical duplicates and ten pairs of field duplicates taken from three test areas in the Abitibi greenstone belt in 1999

Analytical method Number of elements for median RSD Median RSD for analytical duplicates Median RSD for field duplicates
Aqua regia 52 7 11
Cold hydroxylamine 35 11 22
Enzyme Leach 29 21 38
Deionized water leach 49 56 60
MMI 7 (14)* (53)*

Samples of B-horizon soils are composites of sub-samples from five auger holes within a 2 m radius. Duplicate composite samples were collected at a 4 m distance
from the first sample.
*
RSDs for MMI are not directly comparable with that of the other methods. MMI samples are single (not composite) samples taken by auger at a fixed interval
1025 cm below the Ao-horizon. Analytical RSDs for the MMI samples are derived from in-house laboratory duplicates, not blind duplicates as with other
methods.

Table 2. Summary of sites studied during CAMIRO Deep-Penetrating Geochemistry Phase II project, 19992001

Location Deposit type Age Grade Cover Cover thickness Cover age
Chile
Spence Cu Porphyry Paleocene 400 Mt 1.0% Cu Piedmont gravel 3180 m Miocene
Gaby Sur Cu Porphyry Oligocene 400 Mt 0.54% Cu Piedmont gravel 2040 m Miocene
Mansa Mina Cu Porphyry Oligocene 325 Mt 1.0% Cu Piedmont gravel 50>300 m Miocene
Tamarugal False Anomaly n/a n/a Piedmont gravel 300 m Miocene

Nevada
Mike Cu-Au Pre-Tertiary 150 Mt 0.25% Carlin formation 150250 m Miocene
Cu, 0.71 g/t Au
Abitibi
Cross Lake Line 6 VMS Archean n/a Clay 30 m Quaternary
Cross Lake Line 40 VMS Archean n/a Clay and sand 52 m Quaternary
Half-Moon Lake VMS Archean n/a Clay 1215 m Quaternary
Marsh Zone Gold Archean n/a Clay and peat 1027 m Quaternary
Tillex Copper Archean 1.38 Mt 1.6% Cu Clay, till, peat 30 m Quaternary

Table 3. Analytical methods for B-horizon and equivalent soils

Location Deionized Enzyme MMI-A Amm. Hydroxylamine Aqua regia WEM AEM OBM FMM
water Leach acetate
Chile
Spence U U U U U U U U U U
Gaby Sur U U U U U U U U U
Mansa Mina U U U U U U U U
Tamarugal U U
Nevada
Mike U U U U U U U U U
Abitibi
Cross Lake Line 6 U U U U U U U U U U
Cross Lake Line 40 U U U U U U U U U U
Half-Moon Lake U U U U U U U U U
Marsh Zone U U U U U U U U U
Tillex U U U

WEM=Water-extractable, AEM=adsorbed extractable metal, OBM=organic-bound metal, FMM=iron- and manganese-bound metal

Toronto in December 2001 when sponsors approved further Analytical methods. Analysis of soils was on material sieved to <80
work. The additional results were distributed as seven reports in mesh (<0.177 mm). For the deionized water extraction, 20 ml of
October 2002, including isotope studies in Chile, detailed trench water were added to 2.5 g sample and tumbled in a roller for
sampling at Cross Lake, and data provided by IGGE in Beijing. 3 min every 15 min for 1 hour. After settling for 10 min, the
Project results are subject to a two-year confidentiality period leach was centrifuged for 8 min at 2500 rpm, then decanted.
after initial distribution to sponsors. Because of this restriction, Enzyme Leach and MMI-A are patented and proprietary leaches,
some of the results from the November 2001 release and none respectively, described by Hall (1998). For ammonium acetate at
of the data from the October 2002 release could be considered pH 5 (AA5),which dissolves carbonate minerals, 1 g sample was
for inclusion in this overview report. Work funded by the OGS digested by 40 ml of 1.0M NH4OAc/pH 5.0 for two hours,
was not subject to the confidentiality agreement and these then centrifuged and the solution diluted with water 50:1. Cold
results have been presented in OGS publications and elsewhere, hydroxylamine in weakly acidic solution dissolves Mn oxides (HX
which are listed in the references. Because of the volume of Mn). For this, 1 g of sample is treated with 25 ml of a solution
information obtained during Phase II of the project, only with 0.1M NH2OH:HCl in 0.04M HNO3 for 30 min at
selected parts of the work are described here. room temperature. For a limited number of samples involving
18 E.M. Cameron et al.

Table 4. Other methods used at the test sites

Location Ground- Soil gas Soil: Soil: Metals in Soil pH, Soil CO3 Soil SO4 Biogeochemistry Humus, Humus,
water CO2, O2 stable Pb soil gas Cond Na aqua regia
isotopes isotopes pyrophosphate
Chile
Spence U U U U U
Gaby Sur U U U
Mansa Mina U U
Tamarugal U U U U
Nevada
Mike U U U U
Abitibi
Cross Lake Line 6 U U U U U U U U U U
Cross Lake Line 40 U U U U U U U U U
Half-Moon Lake U U U U U
Marsh Zone U U U U U U
Tillex

sequential leaches at Spence and Cross Lake, we also used


ammonium acetate at pH 7 (AA7) and a more aggressive hydroxy-
lamine leach (HX Fe), which dissolves Fe as well as Mn oxides:
hot 0.25M NH2OH:HCl in 0.25M HCl. An aqua regia leach was
also used; this dissolves all secondary minerals in soils. After
dissolution all leach solutions were analysed by ICP-MS and, for
elements at high concentrations, by ICP-ES. It should be noted
that because the MMI-A and hydroxylamine are acidic, they also
dissolve carbonates. Thus, in a non-sequential leach mode, HX
Mn dissolves the water-soluble salts and elements within
carbonates, as well as elements present in Mn oxides.
The WEM (water-extractable metal), AEM (adsorbed
extractable metal), OBM (organic-bound metal) and FMM
(iron- and manganese-bound metal) methods were carried out
at the IGGE in Beijing. These leaches were applied sequentially.
After the first leach, the residue is treated with the second leach
and this is repeated through the third and fourth leaches. The
first leach (WEM) is deionized water. The next leach (AEM) is
ammonium citrate, which removes adsorbed elements. The
third leach (OBM) is sodium pyrophosphate to extract organic-
bound material. The final leach (FMM) is a mixture of
ammonium citrate and hydroxylamine hydrochloride to dissolve
Fe and Mn oxyhydroxides.

Studies in Chile
Study areas in Chile are shown in Figure 14. Spence, Gaby Sur
and Mansa Mina are deposits with substantial reserves of
copper, which are being prepared for mining or are the subject
of feasibility studies. All are covered by piedmont gravels, which
are consolidated rocks of Miocene age. At all sites, there are
distinct geochemical anomalies in soils above the deposits. The
fourth study area is Tamarugal, 50 km NW of Chuquicamata.
Here there is a extensive anomaly, >100 km2, with high
contents of porphyry indicator elements, Cu, Mo, Re, As and
Se. Drilling by Noranda through 300 m of piedmont gravels
showed that the basement rocks below the gravels are barren.
The study of this false anomaly was undertaken to understand
the processes that led to its formation. In this overview paper
we describe selected aspects of our study at the Spence, Gaby
Sur and Mansa Mina sites.

Spence Deposit, Chile. The Spence deposit was discovered by Fig. 14. Map of northern Chile showing the location of major
RioChilex in 199697 by grid drilling through piedmont gravels porphyry copper and other copper deposits. The sites studied where
porphyry copper deposits are covered by piedmont gravels are
of Miocene age. The deposit displays a typical supergene- Spence, Gaby Sur, and Mansa Mina. Another site examined is
enriched sequence and is associated with three dacite porphyry Tamarugal, 50 km NW of Chuquicamata, where a strong anomaly in
stocks (Fig. 15) intruded along a NE axis into andesite. Sulphide soils lies above barren basement covered by 300 m of gravel.
Finding deeply buried deposits using geochemistry 19

depressions to explain the saline zones. Sodium chloride is


involatile, so the most reasonable explanation for its presence in
soils together with other constituents of local groundwater is
that mineralized groundwater reached the surface through the
fracture zones. Where the soil sampling traverse crosses the
deposit, the water table is at 60 to 70 m depth. During
earthquakes in this seismically active region, mineralized
groundwaters were pumped up the fracture zones and flooded
the surface (Cameron et al. 2002).
Sampling of groundwaters from 25 drill holes showed that
waters from the deposit are saline (Leybourne & Cameron
2000a). Waters flowing into the deposit from the east have low
contents of Cu, <50 ppb, whereas in the deposit, contents can
exceed 1000 ppb (Leybourne & Cameron 2000b). Downflow,
Cu content falls to <20 ppb (Fig. 17). High contents of Cu in
groundwater resulting from dissolution of ore minerals are
confined to the area of the deposit because Cu2+ is readily
adsorbed by colloids, limiting its mobility. Copper in soils
(Fig. 16) shows a similarly restricted spatial distribution, with
anomalous amounts occurring in soils above the Spence frac-
ture zone but not over the Eastern fracture zone. By contrast,
porphyry indicator elements that migrate as anions are not
adsorbed by colloids. Selenium, for example, which amounts to
<50 ppb in waters upflow from the deposit, increases to as
much as 700 ppb in the deposit, as a result of oxidation of
sulphide minerals of magmatic origin. This high level continues
in the downflow groundwater plume from the deposit (Fig. 17).
Sulphur isotope data on the groundwater show that sulphides
are actively oxidizing (Leybourne & Cameron 2000a). The
energy thus released appears to be stimulating bacterial activity,
Fig. 15. Outline map of the basement geology of the Spence deposit, possibly including methanogenesis, since there is an unusually
based on drilling carried out by RioChilex. The basement is covered wide range in !13C for dissolved inorganic carbon from "28 to
by 30 to 180 m of piedmont gravels. On the soil sampling traverse, +9 (Leybourne & Cameron 2000a; Cameron & Leybourne
the gap immediately to the east of the deposit is occupied by a road 2002). Although groundwater sampling is rarely used in mineral
and an aqueduct. UTM coordinates are in metres.
exploration, Figure 17 indicates the possible utility of this
method using the far-travelling nature of porphyry indicator
mineralization was formed at 57 Ma, followed by supergene oxyanions.
alteration over a long interval from 44 to 28 Ma (Rowland & The ratio of filtered to unfiltered groundwater samples
Clark 2001). Reserves recoverable by open-pit mining are 50 Mt (Fig. 18) is an eective measure of the mobility of elements in
of oxide ore with 1.4% Cu, 200 Mt of enriched sulphide ore groundwater. Iron and Al readily precipitate as hydroxides to
with 1.3% Cu, and 150 Mt of primary sulphide ore with 0.6% form suspended colloidal particles, which are removed along
Cu. The irregular deposit surface is covered by 30180 m of with adsorbed ions during filtering. These colloids have a
gravels. negative charge, which attracts metal cations such as Pb, Cu, Ce
Soil samples were collected at 1020 cm depth along an and Y, fixing these cations and restricting their movement.
undisturbed eastwest traverse over the centre of the deposit Other metals Re, Mo, V, As, Se form oxyanions, with
(Fig. 15), where gravels are c. 100 m in thickness. Measurements negative charge, that are not attracted to the negatively charged
made in the field during sampling on soil deionized water suspensates. These metals are mobile as anions, along with
slurries identified two zones of high conductivity, one directly conservative cations, such as Na, Ca and Sr. The right-hand side
over the Spence deposit and another 1 km to the east, shown in of Figure 18 is dominated by cations, which either form
Figure 15 as the Eastern fracture zone. High conductivity is due colloidal particles or are fixed to these particles, limiting their
to NaCl (Na is shown in Fig. 16), which elsewhere on the mobility. The left-hand side of the figure comprises metals that
traverse is present in only trace concentrations. The high form oxyanions or by conservative cations, e.g. Ca2+ and Na2+,
conductivity zones also contain higher levels of CaCO3 and neither of which are adsorbed by negatively charged suspended
many elements that are abundant in groundwaters of the region, colloidal particles.
including Br, I, Li, S and Sr plus mobile indicators of porphyry The dierent behaviours of cations and anions are also
mineralization that dissolve as anions: As, Mo, Se and Re. evident at the surface, after flooding by mineralized ground-
Caliche is developed in the soils over the Eastern fracture zone, waters. The rare rains of the region redistributed elements that
but is otherwise absent along the traverse. Trenches dug in the arrived with the groundwaters. Copper as Cu2+ is readily
gravels of the high conductivity zones showed that they are adsorbed, then incorporated into soil minerals; it is retained in
fractured, with north-trending and east-trending sets of vertical the top 20 cm of a vertical soil profile over the deposit
fractures. At a background, low conductivity site, west of the (Cameron et al. 2002), whereas elements that form anions, such
deposit, gravels are unfractured. The fracture zones are inter- as As, and conservative cations, like Na, are removed to depth
preted to represent the upward propagation of basement faults by the rain (Fig. 19).
during the c. 10 Ma interval since the piedmont gravels were Figure 20 shows the proportions of Cu contained in dierent
deposited (Cameron et al. 2002). Pampa over the deposit is bare mineral phases within the same soil profile as shown in Figure
of vegetation and slopes gently to the west; there are no 19. Samples were treated sequentially by four leaches. The first
20 E.M. Cameron et al.

Fig. 16. Plots of Na extracted by deionized water and Cu by deionized water, Enzyme Leach, MMI, ammonium acetate, hydroxylamine (HX
Mn) and aqua regia from an eastwest traverse across the Spence copper deposit, Chile. Horizontal scale (eastings) in metres. The background
concentration of Cu away from the deposit represents the endogenic component and that over the deposit is a mixture of the exogenic and
endogenic phases. The aqua regia leach shows the highest proportion of the endogenic phase and, hence, the poorest anomaly to background
contrast.

was ammonium acetate (AA5), to dissolve Cu present in profile, whereas manganese decreases. These plots indicate that
carbonate. The filtered residues from AA5 were treated with the higher contents of Cu present in the upper 20 cm of the
cold hydroxylamine (HX Mn) to dissolve Mn oxides. The profile are unrelated the abundance of the host phases. The
residues from HX Mn were treated with hot hydroxylamine results of the sequential leaching experiment is an illustration of
(HX Fe) for Fe oxides. The final leach in the sequence was aqua the conceptual model of Figure 11, where Cu derived from the
regia. Anomalous quantities of Cu are confined to the top deposit via the intermediary of groundwater has become
20 cm of the profile; the total concentrations of Cu extracted distributed through a variety of secondary minerals present in
from samples below 20 cm are similar to the contents of Cu by the upper 20 cm of soil, including those only soluble in aqua
aqua regia in the 1020 cm interval in background areas away regia. In the upper 20 cm of the profile all measured phases are
from the deposit (Fig. 16). Separate, i.e. non-sequential, analyses enriched in Cu.
of the samples were done by the Enzyme Leach to provide a
measurement of water-soluble Cu. The amounts extracted by Gaby Sur. Codelcos Gaby Sur porphyry deposit, containing
the Enzyme Leach are small relative to Cu sequestered in 400 Mt at 0.54% Cu, is 43 km east of Spence. It lies at an
minerals, but also show the enrichment of water-soluble Cu in altitude of 2700 m in a broad valley. Like Spence, the climate is
the upper part of the profile. This profile, like most others hyper-arid. Supergene-enriched copper oxides, up to 180 m
observed at Spence, shows no clear dierentiation into horizons thick, are underlain by hypogene sulphides (Fig. 21). The
either by colour or composition; the soils are reddish-brown deposit lies in a graben, delimited by high-angle boundary faults
throughout and are not layered with calcrete. The plots to the and is covered by up to 40 m of gravel, deposited at c. 9.6 Ma
right of Figure 20 represent the amounts of the dierent host (Camus 2001). The upper 20 m of the gravel is cemented by
phases extracted during the sequential leaching: Ca representing calcrete, making it impermeable to water where unfractured.
carbonate, Mn representing manganese oxides an Fe represent- Water is found only below the basement unconformity, i.e. at
ing iron oxides. Carbonate and iron oxides increase down the >40 m depth, where drill holes intersect major faults.
Finding deeply buried deposits using geochemistry 21

Fig. 17. Copper and Se contents of


groundwaters from within and near the
Spence deposit, Chile. Squares are drill
holes where groundwater was sampled,
with analyses as shown.

complex than those at Spence due to the presence of calcrete


and gypcrete. The sampling procedure was dierent from
Spence and followed the Codelco procedure of taking
red-coloured, Fe-rich soil from within the top 1030 cm of the
profile. In the soils over both boundary faults there are distinct
anomalies for water-soluble Na (Fig. 21) and Cl and for
elements similar to those found to be anomalous at Spence: As,
I, Mo, Se and Re. In soil pits, the calcrete-cemented gravels are
fractured in these saline zones, also similar to Spence. These
features are attributed to pumping of mineralized groundwater
to the surface up the boundary faults and through the overlying
fractured gravels during earthquake activity, followed by
Fig. 18. Ratio of concentrations of elements in filtered to unfiltered
evaporation (Cameron et al. 2002).
groundwaters, Spence deposit. Analyses for Cu by dierent extractions are shown in
Figure 21. The results by the weakest leaches, deionized water
and the Enzyme Leach, show clear anomalies over both
Soils were sampled along an undisturbed eastwest traverse boundary faults, with a high anomaly to background contrast.
across the deposit, with samples at 50 m intervals over the These anomalies are coincident with the peaks for Na (and Cl).
deposit and 100 m intervals on the flanks. The soils are more The similarity in the amounts of Cu extracted by deionized

Fig. 19. Distribution of Cu, Na and As in a vertical soil profile over the Spence deposit from the surface to 100 cm depth. There are no readily
discernible soil horizons. Extraction by hydroxylamine (HX Mn). Prior to sampling the profiles, the top few centimetres of the surface was
removed so as not to include any contaminated material.
22 E.M. Cameron et al.

Fig. 20. Vertical soil profile directly above the Spence deposit. On the left are the amounts of Cu in ppm extracted sequentially by: (1) ammonium
acetate (AA5) dissolving carbonate, (2) cold hydroxylamine (HX Mn) dissolving manganese oxides, (3) hot hydroxylamine (HX Fe) dissolving
Fe oxides, (4) aqua regia. In the centre is Cu in ppb by Enzyme Leach, extracting water-soluble material. On the right is (a) Ca extracted by
ammonium acetate (AA5), (b) Mn extracted by cold hydroxylamine (HX Mn), (c) Fe extracted by hot hydroxylamine (HX Fe).

water and Enzyme Leach indicates that the latter is extracting (Fig. 22). The fault that cuts the deposit, and forms its eastern
mainly water-soluble Cu. The anomalous zones above the faults boundary, is the West Fault, a major strike-slip fault of regional
that bound the deposit are poorly defined by the stronger extent that may have had an influence in localizing the
leaches. Ammonium acetate at pH 5 (AA5) dissolves Cu present important cluster of porphyry deposits in the Chuquicamata
in carbonate minerals. Background concentrations of Cu by the area (Fig. 22). Mansa Mina is an elongate, steeply dipping
AA5 leach are an order of magnitude higher than for the two deposit (Fig. 22), containing a mainly hypogene assemblage.
weaker leaches that extract water-soluble material only and Sulphides account for 300 Mt at 0.95% Cu and oxides 25 Mt at
these additional amounts of Cu obscure the Cu derived from 1.11% Cu. The deposit is up to 300 m in width and over 1000 m
the mineralized groundwaters that reached the surface. Copper in vertical extent and comprises four steeply dipping panels that
present in carbonate is thus largely of endogenic origin, derived are delimited by faults subsidiary to the West Fault (Sillitoe
from primary minerals in the gravel soils. The cold hydroxy- et al. 1996). The easternmost panel is barren, comprising
lamine leach (HX Mn) dissolves Mn oxides, plus carbonate chloritized and pyritized andesitic flows. Panels 2 and 3 are of
minerals, plus water-soluble salts. Cumulatively the first two of sericitized granodiorite containing pyrite-poor, copper porphyry
these phases have a high content of Cu of endogenic origin, mineralization. Panel 4 is also highly altered granodiorite, with
giving a background concentration of Cu approximately 50 sericite and advanced argillic alteration, with a enargite- and
times higher than Cu extracted by deionized water or the bornite-rich high sulphidation assemblage. There has been
Enzyme Leach. Again, this obscures the Cu of exogenic origin. supergene alteration, forming a leached zone and a partially
For the aqua regia extraction, the background concentration of oxidized zone above the sulphide zone. The upper part of the
Cu reaches 2000 times that of the deionized water and the sulphide zone has been enriched by chalcocite. The deposit is
Enzyme Leach, again obscuring Cu derived from the deposit via entirely covered by Miocene gravels, the minimum thickness of
mineralized groundwaters. Note, however, that one sample of these being 50 m on the west side of the West Fault and several
soil situated at 517450E, above the west boundary fault, has hundred metres on the east side. Depth to the water table is not
high contents of Cu by both hydroxylamine (HX Mn) and aqua known.
regia. This high concentration suggests that, like Spence, there Mansa Mina lies between the towns of Calama and
has been a long period of pumping of mineralized groundwaters Chuquicamata and immediately east of the highway linking
to the surface and the incorporation of Cu of exogenic origin these centres. Only a limited length of undisturbed ground was
into secondary minerals. available for a sampling traverse across the deposit (Figs 22, 23)
between the highway and gravel dumps to the east. Samples
Mansa Mina. Mansa Mina is a faulted slice of porphyry were taken at irregular intervals to avoid vehicle tracks. The
mineralization, possibly from the nearby Chuquicamata deposit ground slopes gently from north to south. Soils are marked by
Finding deeply buried deposits using geochemistry 23

Fig. 21. Plots of Na extracted by deionized water and Cu by deionized water, Enzyme Leach, ammonium acetate, hydroxylamine and aqua regia
for soils from an eastwest traverse across the Gaby Sur copper deposit, Chile. Horizontal scale (eastings) in metres.

strong development of both gypcrete (near the surface) and


calcrete, which first occurs at depths between 20 and 40 cm.
Samples were taken immediately above the calcrete horizon to
minimize inclusion of gypcrete. Results of Enzyme Leach
analyses show a strong spike anomaly for Cl (Fig. 23) and Na
in the soil immediately above the West Fault. There is a
coincident spike anomaly for Se (Fig. 23). All samples contain
S, because of the presence of gypcrete, but the gypcrete has a
low Se content, and the median ratio for Se$1000/S across
the entire traverse is 0.07, in the range of ocean water. For the
sample directly above the West Fault the ratio is 1.9, in the
range of the oxidation products of igneous sulphide. The same
sample is anomalous in Re (31 ppb by Enzyme Leach, 48 ppb
by aqua regia), an indicator element for copper and copper
molybdenum porphyries, since it mainly occurs as an impurity
in molybdenite. Other elements that are strongly anomalous in
this sample are Br and I, typical constituents of groundwaters of
the region, and K, Rb and Tl, which are abundant in sericitic Fig. 22. On the left is an eastwest cross-section across the Mansa
alteration. An anomaly for Mo (Fig. 23) and Cu are displaced Mina deposit after Sillitoe et al. (1996). The unpatterned area between
the sulphide zone and the fault is barren rock. On the right is a map
60 m to the east. The results suggest that mineralized ground- showing the spatial relationship between the West Fault and the
water has been pumped up the West Fault during seismic cluster of copper porphyry deposits in the Chuquicamata area. For
activity, followed by its evaporation at the surface. location of area shown, see Figure 15.
24 E.M. Cameron et al.

Fig. 24. Map showing the Carlin Trend (shaded) and some of the 40
gold deposits found along this trend.

localized by structural features. The evidence is consistent with


groundwater having been forced to the surface up fracture
zones by earthquake-induced (seismic) pumping.

Studies in Nevada
More than 40 Au occurrences within the Carlin Trend in
northeastern Nevada (Fig. 24) form the largest accumulation of
mineable Au in North America. One of these is the Mike
deposit.

Mike Deposit. This deposit, hosted by sedimentary rocks of


Palaeozoic age, was discovered by Newmont Corporation in
1989 while drilling on the predicted extension of the NW-
trending Good Hope fault (Fig. 25) into an area with a thick
cover of Carlin Formation of Tertiary age. The intersection of
this fault with NE-trending faults was the primary structural
Fig. 23. Analyses of Cl, Se and Mo by Enzyme Leach in soil samples control for the previously discovered Tusk and Gold Quarry
from a westeast traverse across the Mansa Mina deposit at deposits. The Good Hope fault is the boundary between two
7526500N. portions of the Mike deposit: the Main Mike, containing
43.2 Mt of 0.034 oz/t Au and 76 Mt of 0.22% Cu; and the West
Summary of observations and interpretation at Chilean sites. At all three Mike containing 110 Mt of 0.025 oz/t Au and 74 Mt of 0.28%
sites there is evidence of saline groundwater having reached the Cu.
surface and evaporated. In addition to Na and Cl, zones in soils Copper mineralization consists of a sub-horizontal supergene
are enriched in elements typical of groundwater in the region, I oxide and sulphide blanket up to 120 m thick that mainly
and Br, and porphyry indicator elements, Se, Re, Mo and Cu. underlies, but also overlaps, Au mineralization. Supergene
Over the Spence deposit enrichment occurs above a fracture processes may have caused the mobilization of Cu to greater
zone in the gravels, and above a water table at 6070 m depth. depths than Au. Teal & Branham (1997) note enrichments in
At Gaby Sur the groundwater signature is seen in soils above the ore of Cu, Au, Zn, Ag, Bi, Mo and Te; in addition, Cd and
the boundary faults of the deposit; the water table is at >40 m Se may be enriched. The deposit is covered by up to 240 m of
depth. At Mansa Mina the groundwater signature occurs Carlin Formation of Eocene age comprising piedmont gravel,
directly above a major fault in the basement below the gravel finer clastic sediments, waterlain tu and a basal conglomerate
cover. The depths of the present water table at Spence and and regolith that contains mineralized (oxidized) clasts. A
Gaby Sur are too great to permit groundwater to be raised to perched water table in the Carlin Formation is c.50 m below the
the surface by capillarity. In a coarse-grained medium, such as surface and a second aquifer is in the Palaeozoic rocks (Jackson,
gravel, soil suction can draw water up only a few metres at best. 2000).
Moreover, given the permeable nature of gravel, groundwater The simplest mechanism for generating geochemical
raised by capillarity would extend over a wide area and not be anomalies through 240 m of post-mineral cover is by the
Finding deeply buried deposits using geochemistry 25

Fig. 25. Distribution of copper mineralization in the Mike deposit in Fig. 26. Topography of the immediate Mike area, with contours at
relation to major faults in the basement, shown by dashed lines. 25 ft intervals. The dashed lines show interpreted Pleistocene faults
Information courtesy R.G. Jackson and Newmont Corporation. Solid in the Carlin Formation, based on the criteria of Dohrenwend &
NNE lines show two interpreted Pleistocene faults that cut the Carlin Moring (1991), who defined an orientation of 028o, as shown by
formation and intersect the sampled Line 3 (see Fig. 27). the arrow. These interpreted faults intersect the sampled Line 3 at
sites A and B.

movement of fluids or gases up faults in this cover.


Dohrenwend & Moring (1991) carried out photo-geological Enzyme Leach results for Au for this line are below the
interpretations of recent faulting in this region. Of several detection limit, but this extraction also shows an anomaly on
criteria used to distinguish faulting, the most relevant to the the east side of Channel B. For Cu, the results by the four
Mike area is: prominent alignments of linear drainageways, extractions are shown in Figure 28. The Channel B anomaly is
ridges and swales, active springs or spring deposits, and linear shown clearly by the three leaches that extract the most Cu
discontinuities of structure, rock type, and vegetation. This aqua regia, hydroxylamine (HX Mn) and MMI but the
faulting, which they assign to early to middle Pleistocene time anomaly is not apparent in the Enzyme Leach results.
(0.13 to 1.5 Ma), with a mean orientation of 028o, results in In an earlier section we have discussed anomaly formation as
dissection of the surface along faults of greater than 10 m. The an incremental process, with metal being introduced in water-
topography of the Mike area (Fig. 26) shows deeply incised dry soluble form and then progressively incorporated into the
stream beds with an orientation close to 028o. Based on this secondary minerals of the soils. If the anomaly associated with
topography, two faults in the Carlin Formation are interpreted Channel B is related to Pleistocene faulting of the Carlin
to intersect the sampled Line 3. The fault to the NW, Channel Formation, then the anomaly has had up to 1.5 Ma to form.
A, is marked by a stream and floodplain. Channel B was dry This time span may account for the strong response shown by
during our visits. Its east slope is precipitous, which may the aqua regia extraction, which dissolves most secondary
indicate a fault scarp. minerals in the soil. Anomalies can also, presumably, stop
Climate is semi-arid, with sparse sagebrush vegetation. Soils developing when new batches of elements in water-soluble
were collected along Line 3 from sites at 30 m intervals; at each form are no longer introduced. This may account for the
site, samples were taken from a depth of 4050 cm from five anomaly response of the Enzyme Leach, which extracts water-
holes dug within a radius of 1.5 to 3 m. The sampling depth was soluble metal, being lesser than that of the stronger leaches that
selected on the basis of earlier studies by Jackson (2000). The dissolve secondary minerals.
five samples were mixed to form a composite sample. Soils are Other elements that show strong anomalies on the steep
immature with a weak B-horizon below 1530 cm. Relatively west-facing slope of Channel B include Mo by aqua regia, Cd by
little carbonate was found along this line and soils are mostly hydroxylamine (HX Mn), Zn by MMI and by aqua regia, and
low in organic material, except in the alluvial soils around the Hg by aqua regia. Elements that are anomalous in the soils are
stream that marks Channel A. those enriched in the ore, so that their ultimate source in the
Figure 27 shows results for Cd, Cu, Mn and Au by aqua deep mineralization is a reasonable supposition. Elements that
regia. There are anomalies for Cd in the alluvial soils centred are not components of the ore, such as rare earth elements, do
over Channel A. However, the strongest anomaly for Cd is at not have anomalous patterns in the soil. Jackson (2000), after
Channel B, located in residual soils of the steep west-facing collecting samples on a wide-interval grid over Mike, found that
(scarp?) slope of the dry valley, not in the vicinity of the several elements were depleted across the top of the deposit,
stream-bed. Copper and Au are anomalous only on Channel B. notably Mn; this was confirmed by our sampling (Fig. 27).
The highest value for Au by aqua regia, at 17 ppb, is 9 times the Jackson suggested that elements may be transported to the
median value of 1.9 ppb, the median being a reasonable proxy surface laterally and vertically around the deposit to create
for the local background. Selective leaches were also used. The a central low with flanking highs. Manganese oxide is a
results by hydroxylamine (HX Mn) are mostly below the redox-sensitive mineral that may be dissolved in a reducing
detection limit of 0.05 ppb Au. The MMI maximum value of environment. A sulphide deposit is a large mass of reduced
6.2 ppb Au over Channel B is 14 times the median. Many of the material, which, when oxidized, must reduce an equivalent mass
26 E.M. Cameron et al.

Fig. 27. Analyses for Mn, Cu, Au and


Cd by aqua regia in soils from Line 3
across the Mike deposit. Note that the
horizontal axis is in feet, corresponding
to the original Newmont survey.

Fig. 28. Analyses for Cu by aqua regia,


hydroxylamine, MMI-A and Enzyme
Leach in soils from Line 3 across the
Mike deposit. Note that the horizontal
axis is in feet, corresponding to the
original Newmont survey.

of oxidized material. So a possibility exists that the Mn low over similar to data obtained over the Carlin Trend by McCarthy &
the deposit is a remote product of the oxidation of Mike McGuire (1998). Higher "CO2 values and corresponding lower
sulphides, i.e. a reduced chimney. But elements that are not values for "O2 were found both over the deposit and in areas
redox sensitive also show a low over the deposit: Cs, Ti, Zr and remote from it, but the survey was not extended to where Line
Al. So facies change in the Carlin Formation to a sandier 3 intersects Channel B, the area of strongest metal response.
sediment overlying the deposit, and more enriched in resistate The low delta values and anomalous values away from the
(heavy) minerals, may explain some of the geochemical results. deposit, make it is dicult to judge whether variation is due to
In addition to the analyses of the soils by selective leaches, deep mineralization, or near-surface features, or normal varia-
other studies were carried out. In July 1999, a CO2 O2 soil gas tions of gas within soils.
survey was carried out at 159 sites on three lines by Patrick Pauwels et al. (1999) described a method for the collection of
Highsmith and Mary Doherty. The sampling depth for the metals in soil air using activated carbon held inside a bag of
probe was c. 40 cm and the principal sampling interval was Gore-Tex within in a cylindrical plastic container. They carried
30 m. Repeated measurements at a base station showed that soil out orientation surveys in southern Spain, where measurements
gas concentrations were stable during the sampling period. of CO2, He and Rn showed that gas is emanating from fractures
Delta values were calculated relative to atmospheric concen- that cut ore bodies in the Iberian Pyrite Belt. Collectors were
trations for these gases. For "CO2 the range was 0.08 to 0.93%, installed in the soils and recovered after 100 days. Elution and
with a median of 0.46% and for "O2 the range was "0.1 to analysis of the activated carbon from the Iberian Belt showed
"0.8%, with a median of "0.35%. There is an inverse metal anomalies coincident with CO2 anomalies. Courtesy of
correlation between "CO2 and "O2, which is consistent with Philippe Freyssinet of BRGM, similar collectors were installed
the consumption of O2 to produce CO2. The amount of CO2 on Line 3 at the Mike deposit in May 2000 and retrieved in
is lower than values reported by Lovell & Hale (1983) for soil August 2000. The collectors were placed at the top of a 50 cm
gas over a variety of massive sulphide mineralization, but is length of PVC pipe inserted into auger holes, leaving the
Finding deeply buried deposits using geochemistry 27

Fig. 29. The western portion of the Abitibi greenstone belt (shaded)
showing the location of the four study sites. Much of the area to the
west of Rouyn-Noranda and Matagami has a discontinuous cover of
fine-grained glaciolacustrine sediments.

collectors above ground. Forty-four collectors, including


duplicate sites, were installed and three blank collectors were
retained within plastic bags. Two of these blanks were kept in
the field and one in the laboratory. After shipping to BRGM,
the carbon was eluted and the solution analysed by ICP-MS.
Contents above the detection limit were obtained for As, Cr,
Co, Cu, Ni, Pb and Zn. However, in all cases, the contents
obtained from the collectors installed in the field were no
dierent from the blanks, i.e. no measurable amounts of metal
were detected in soil air. Similar collectors were installed in the
piedmont gravel soils of the fracture zone above the Spence Fig. 30. Geological cross-section along Line 6 at Cross Lake, based
on diamond drill hole data by Cross Lake Minerals Ltd and
deposit and at a background location west of the deposit. These overburden drilling by Ontario Geological Survey. Superimposed are
were retrieved after one year. Elution and analysis of the carbon a spontaneous potential (SP), ORP measurements of redox con-
showed that metals were no more abundant at the sites over the ditions at 1.5 m below water table with a two-minute reading,
deposit than at the background sites. carbonate content of B-horizon soils, and Zn content by MMI
analysis of soils taken at a depth of 10 to 25 cm below the base of
decomposing vegetation.
Note added in proof
Newmont carried out a major drilling program at the Mike
deposit from 1997 to 2000 and the results have been described
by Norby and Orobona (2002). The principal soil anomalies at such as the Kidd Creek volcanogenic massive sulphide (VMS)
location B (Fig. 27) are now known to occur at the surface deposit near Timmins, the Hollinger, Dome and McIntyre Au
intersection of the Nebulous fault, a NNE-trending post-Carlin deposits at Timmins and the Lake Shore and Kerr-Addison Au
fault. In addition to cutting the Carlin Formation, it cuts and deposits near Kirkland Lake. Much of the belt has a dis-
displaces the goldcopper oxide zone, and a lower sulphide continuous cover of glaciolacustrine clays and other fine-
zone at c. 500 m depth now described by Norby and Orobona. grained glacial sediments (Fig. 29). Most of the known deposits
The top of the sulphide zone is distinguished by a 60 m thick are exposed in windows in this glacial cover. There is reason to
blanket of sphalerite-rich rock. Cadmium is a common trace expect that undiscovered deposits lie hidden beneath glacial
constitutent of sphalerite. This explains why Cd shows such a sediments. We here discuss some of the results for one of the
clear anomalous pattern (Fig. 27) above a goldcopper deposit. sites, Cross Lake.
There is localized oxidation of the sulphide zone where it is
intersected by the Nebulous fault. Other elements present in the Cross Lake. The Cross Lake VMS mineralization of Archean
sulphide zone, including Zn, Ag, As and Ni, are also anomalous age, located 50 km SE of Timmins, is similar in mineralogy,
in the soils along the scarp slope of the Nebulous fault. The composition and age to the well-known Kidd Creek ZnCuAg
elements are interpreted to have moved 500 m up the fault from deposit. Host rocks are felsic pyroclastic rocks, intruded by
the sulphide zone. Recent isotopic studies by Dublyansky et al. feldspar porphyry and diabase dykes. The immediate host is tu,
(2003) at the Yucca Mountain nuclear waste disposal site, also lapilli tu and chert, with sericitic and chloritic alteration. On
in Nevada, have shown that fluids of deep-seated origin have Line 6 (Fig. 30), sulphides in the mineralized lens are, in order
moved up several hundred metres through a thick vadose zone of abundance, pyrite, honey-coloured sphalerite, chalcopyrite
along a permeable fault. and galena. Zinc dominates over Cu with assays as high as 26%
compared to a maximum of 1.3% Cu. The width of the VMS
subcrop underlying Line 6 is about 25 m and is covered by 30 m
Studies in Ontario of varved clay with silty laminae that was deposited in a glacial
Four sites were studied in the Abitibi greenstone belt of Ontario lake c. 8,000 years. The area is wet, with groundwater close to
(Fig. 29). This belt is host to a number of world-scale deposits, or at the surface in low areas.
28 E.M. Cameron et al.

Fig. 31. Analyses for Zn and Cd by


Enzyme Leach and Ca by ammonium
acetate on soil samples taken from the
upper 10 cm of B-horizon and the
1020 cm interval of B-horizon along
Line 6 at Cross Lake. Also shown are
pH values for soil-water slurries. The
VMS subcrop is beneath 30 m of silty
clay and extends from 175 m to 200 m
along Line 6. Locations of samples A,
B and C for the 010 cm interval of the
B-horizon (see lower left plot) relate to
Figure 32.

A spontaneous potential (SP) survey showed a low of 15 mV The location of the samples is shown in Figure 32. Sample A
directly over the sulphides (Fig. 30). Initial sampling at sites is from a background area, whereas samples B and C overlie the
25 m apart of soils taken from a thick 20 cm interval of the mineralization. The abbreviated headings for the dierent
B-horizon and also of humus (H), followed by analysis by a sequential leaches are explained in the text.
variety of methods, gave only weak base metal anomalies over The Zn analyses by this leach show a strong anomaly/
the mineralization. But there is a pH low for soil-water slurries background contrast between samples B and C over the
over the mineralization and strong peaks for Ca, Mg and CO3 mineralized subcrop compared to background sample A. After
on the flanks of the pH low. Unweathered clay contains leaching with AA7, the sample residues were treated with
carbonate, but this is removed during the formation of ammonium acetate at pH 5 (AA5). This is a stronger extractant
B-horizon soils. Thus the carbonate peaks in the soils flanking for carbonate, but little, if any, carbonate is inferred to have
the pH low is unusual for B-horizon soils in this clay terrain. remained after the previous treatment, since the amounts of Ca
Separate soil samples were collected specifically for MMI extracted are low. This leach extracts more Zn that AA7 and the
analysis over a constant interval 10 to 25 cm below decaying anomaly/background for AA5 is greater than for AA7. The
vegetation. These samples were mainly B-horizon with an next leach, cold hydroxylamine (HX Mn), extracts Mn oxides.
admixture of Ae and/or Ah soil at some sites. They showed This leach dissolves more Zn from samples B and C than from
distinct Zn anomalies over the mineralization that were absent background sample A, but the anomaly/background contrast is
in the B-horizon samples collected over a thicker and deeper less than either of the acetate leaches (Table 5). The next leach,
interval from that horizon. These disparate results for two sets hot hydroxylamine (HX Fe) dissolves Fe oxides. This extracts
of samples collected at the same time from the same sites substantially more Zn than any of the preceding leaches, but
suggested a depth control on Zn contents in the soils. this is endogenic material, not derived from the mineralization,
Follow-up sampling over a restricted length of the traverse, and no anomaly is apparent over the mineralized zone. The fifth
centred on the mineralized interval, collected (a) the upper leach, aqua regia, presents a similar pattern, with much Zn
010 cm interval of the B-horizon and (b) the 1020 cm interval extracted, but no anomaly.
of the B-horizon. The results (Fig. 31) show that anomalous Comparative data are given in Table 5 for separate (non-
levels of Zn are confined to the uppermost part of the sequential) analyses by the Enzyme Leach and MMI-A. Enzyme
B-horizon, being absent in samples taken immediately below. Leach extracts less Ca, somewhat less Mn, and an equivalent
Sequential leach analyses were carried out by the Geological amount of Fe to leach AA7. Less Zn is extracted by the Enzyme
Survey of Canada on selected samples from the 010 cm Leach than AA7, but the anomaly/background contrast is
interval of the B-horizon. These samples (Fig. 32, with locations high. No major elements are reported with MMI-A analyses.
shown on Fig. 31) comprise sample A from a site away from However, the anomaly/background contrast for Zn by MMI-A
the mineralization and samples B and C directly above the is excellent. The data shown in Table 5 and Figure 32 illustrate
mineralized subcrop. The first leach in the sequence was the eectiveness of weak leaches in selectively extracting the
ammonium acetate at pH 7 (AA7). This dissolves carbonate exogenic phase of an indicator element and separating this
minerals plus water-soluble elements. There is very little car- from the much more abundant endogenic phase that is derived
bonate in the samples, as shown by total CO3 concentrations of from the primary minerals of the clay sediment, the parent of
ranging from 300 to 800 ppm for the three samples. Neverthe- the soil.
less, this leach dissolves what carbonate is present, as shown by Concurrent with the soil sampling, drilling was carried out by
analyses for Ca (Table 5). the Ontario Geological Survey. Shallow boreholes were drilled
Finding deeply buried deposits using geochemistry 29

Fig. 32. Zinc in ppb by sequential leaches of background sample A and samples B and C over a VMS subcrop below 30 m of clay. Samples
are from the upper 10 cm of the B-horizon, Line 6 at Cross Lake. Locations of samples are shown in Figure 31, Zn plot. Upward projection
of the VMS subcrop is indicated by the hatched block.

to 9 m depth to characterize the overburden and subsurface oxidized, e.g.: Fe2+ + YO2 + 2H2O h Fe(OH)3 + H+.
geochemical, pH and redox conditions. Lower redox values, as Formation of hydrogen ions lowers the pH of the soils at and
measured by ORP, outline a reduced column in the clay above the water table, dissolving CaCO3, which migrates
substrate above the mineralization (Fig. 33). This feature is laterally and precipitates on the flanks of the reduced zone in
replicated at the Marsh Zone site. Below the water table, pH is areas of higher pH. The reduced column must include base
relatively constant in a neutral to weakly alkaline range, e.g., at metals present in the sulphide mineralization, most notably Zn
1.5 m below the water table the pH ranges from 7.1 to 7.8. But and Cd, which show as anomalous concentrations in a narrow
at the water table and above there is a substantial drop in pH zone at the top of the B-horizon (Fig. 31). The width of the
directly over the mineralization, to values as low as 5.0. acidic zone and anomalous levels of Zn and Cd in the upper
Fieldwork at Cross Lake provided an opportunity to test B-horizon are 65 to 70 m, with sharp boundaries (Fig. 31).
the model of Hamilton (2000). The empirical observations Given the estimated width of 25 m for the VMS lens at the
summarized in Figure 31 show a close similarity to the subcrop beneath 30 m of clay, the upward dispersion of
theoretical predictions summarized in Figure 5. Oxidation of material is fairly narrowly constrained. Substantial amounts of
the sulphides at depth, suggested by SP lows, releases a rising reduced material are involved to create the zones of low pH and
column of reduced material. Below the water table, access to dissolve carbonate at the surface. Lead extracted from the soils
oxygen and other oxidized species is restricted, but where the above the mineralization is less radiogenic than that sampled
column intersects the water table, the reduced species are away from the mineralization (Cameron et al. 2001). This

Table 5. Data for Ca, Mn, Fe and Zn for a series of sequential leaches and for two single leaches of samples from the 010 cm interval of the B-horizon on Line 6 at Cross Lake.

Sequential leaches Single leaches


Sample AA7 AA5 HX Mn HX Fe Aqua regia Enzyme Leach MMI-A
Ca (ppm)
A 1710 288 654 294 1513 205
B 560 106 62 65 1039 142
C 490 84 213 135 1032 99
Mn (ppm)
A 1.2 5.1 48 64 100 1.1
B 4.1 5.2 3.5 46 79 2.1
C 2.2 2.5 2.0 39 76 0.9
Fe (ppm)
A 2.2 23 118 2800 11400 2.7
B 14 164 344 4500 7900 15
C 10 135 252 3600 7200 10
Zn (ppb)
A 42 103 303 8200 25000 7 64
B 435 1500 970 7700 19100 270 1930
C 317 1410 590 7400 18700 186 1670

The location of the samples is shown in Figure 32. Sample A is from a background area, whereas samples B and C overlie the mineralization. The abbreviated
headings for the dierent sequential leaches are explained in the text.
30 E.M. Cameron et al.

elements is orders of magnitude slower than the downward


movement of water films. The only possibilities for the upward
transport of elements are mass (advective) transfer of water plus
dissolved constituents, or air plus indicator gases or aerosols.
The most striking example of advective transport is in
Chile where the earthquake-induced (seismic) pumping of
mineralized groundwater to the surface through fracture zones
is recognized. The assemblage of elements found in the soils
above fracture zones is similar to that found in groundwaters
and, at Spence, Cu in soils and Cu in groundwaters at
60 m depth are only anomalous in the vicinity of the deposit.
Faults or fracture zones are an essential conduit for bringing
mineralized groundwater to the surface and we find a spatial
Fig. 33. Model for development of anomalies through clay cover correlation between anomalies in soils and neotectonic
incorporating empirical observations from the Cross Lake test site. structures, which appear to represent reactivation of more
There is a reduced column rising above the sulphide subcrop through ancient faults. In Nevada, at the Mike deposit, covered by
the clay cover. At and above the water table, metal ions in this 240 m of Carlin Formation, we also find strong anomalies
reduced column are oxidized by infiltrating oxygen, which generates associated with interpreted neotectonic structures, but here we
hydrogen ions. The resulting low pH environment dissolves carbon-
ates from C-horizon clay soils and this carbonate is reprecipitated on have no evidence of the transport mechanism.
the flanks of the zone of low pH. The Zn2+ and Cd2+ ions are The Abitibi region stands in diametric contrast to Chile and
inferred to have migrated upwards in the reduced column because Nevada: the glacial clay and sand that cover bedrock are only a
anomalous amounts have accumulated in a narrow zone at the top of few thousand years old, lack fracturing, and are water-saturated
the B-horizon. to near the surface. Here too soils show clear signs of buried
mineralization and the empirical observations are remarkably
suggests that Pb2+, as well as Zn2+ and Cd2+ are being similar to those predicted by the model of Hamilton. This
transferred upwards in the reduced column, because of the involves oxidation of the buried sulphide mass and the upward
non-radiogenic nature of Pb present in VMS, compared to that transfer of reduced material, including base metals. At the water
of clay. Trenching showed that tree roots do not penetrate table this reduced material reacts with O2, creating an acidic
deeper than the water table, indicating that roots are not environment that dissolves and redistributes carbonate
involved in the advective transfer of mineralized groundwater originally present in the clay. The substantial flux of reduced
from depth to the surface. Given the short length of time since substances to the surface, the elevated concentrations of Zn and
the glacial sediments were deposited, c. 8,000 years, and the low Cd in the soils over mineralization, bulges in the piezometric
rates cited above for chemical diusion, diusion cannot be the surface, and temperature increases of groundwater at the same
principal means for moving reduced material to the surface. locations cannot be accommodated by diusion processes;
Despite the close coincidence between the Hamilton additional mechanisms are required to explain the empirical
theoretical model and empirical observations, the high Zn and data.
Cd concentrations in the soils above the reduced column Barometric pumping provides a means for the rapid
cannot be easily accounted for by electrochemical processes. transport of air plus gas or aerosols. At the Mike deposit,
These elements are usually mobile as Zn2+ and Cd2+, which are Nevada, tests of the metal content of soil air using collectors
not redox-active; in this form their migration should not containing activated carbon failed to detect greater amounts of
determined by redox gradients. Hamilton et al. (2001, 2002) metal than blank collectors sealed in plastic bags. Similar tests in
reported further intriguing data from the drilling studies at the piedmont gravel soils on the fracture zone above the Spence
Cross Lake. Over the mineralized zone there is an upward deposit also failed to detect metal concentrations that were
bulge in the piezometric surface of close to 50 cm on both greater than a nearby background area. At Mike, CO2 and O2
lines, despite downward hydraulic gradients between the over- measurements in soil air showed variation, but it was not
burden and bedrock piezometers. Near-surface groundwater possible to conclude that these were related to the deposit.
also shows an increase of c. 1%C over the mineralized zone; There is a need to carry out tests on air/gas mixtures released
measurements that have been replicated at dierent times. from fractured rock over known mineralization to identify the
Similar features have been noted at the Marsh Zone and other constituents present.
sites where reduced columns are documented within otherwise By far the most widely used geochemical method for the
oxidized overburden. Much remains to be done to understand discovery of buried deposits is selective leach analyses of soils;
transport mechanisms and to better define changes in tempera- this study has focused on these methods. We argue that
ture and the piezometric surface that may be related to geochemical anomalies in soils over buried mineralization form
mineralization. This is being undertaken as part of a successor incrementally. Metals of external, exogenous origin enter the
project at Cross Lake led by G.E.M. Hall and funded by the soil in water-soluble form and are progressively incorporated
Ontario Mineral Exploration Technology programme and the into secondary minerals, such as carbonates, and iron and
Geological Survey of Canada. manganese oxides. In the case of the Chile and Nevada test
sites, the time available for anomaly formation may have been
a million years, or longer. At these sites there has been time for
CONCLUSION metal of exogenous origin to be incorporated in a variety of
In the Deep-Penetrating Geochemistry project we have secondary minerals. Thus the anomalies can be detected by a
considered the theoretical basis for the upward movement of strong leach, aqua regia, which dissolves all secondary minerals,
material from buried deposits and have carried out field tests in although the anomaly/background contrast is less than for
Chile, Nevada and Ontario to examine transport processes and selective leaches that target specific secondary minerals. In the
compare methods for detecting anomalies. For arid or semi-arid clay-covered terrain of the Abitibi region, several thousand
areas, with a thick vadose zone, upward diusion of dissolved years only have been available for anomaly formation. In this
Finding deeply buried deposits using geochemistry 31

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