An overview of vis-nir-swir field spectroscopy - Spectral International
An overview of vis-nir-swir field spectroscopy - Spectral International
An overview of vis-nir-swir field spectroscopy - Spectral International
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AN OVERVIEW OF VIS-NIR-SWIR<br />
FIELD SPECTROSCOPY AS APPLIED<br />
TO PRECIOUS METALS<br />
EXPLORATION<br />
By<br />
Phoebe Hauff<br />
________________________________________________________________<br />
Page 1
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AN OVERVIEW OF VIS-NIR-SWIR FIELD SPECTROSCOPY AS APPLIED TO<br />
PRECIOUS METALS EXPLORATION<br />
Phoebe L. Hauff<br />
<strong>Spectral</strong> <strong>International</strong> Inc., P.O. Box 1027, Arvada, CO., 80001<br />
303 403 8383 pusa@rmi.net www.pimausa.com<br />
ABSTRACT<br />
Field portable Reflectance Spectroscopy has made a major impact on the<br />
exploration industry because it has changed the way geologists think about their<br />
rocks and about the different alteration systems and relationships between<br />
associated minerals. It has opened new <strong>vis</strong>tas for the <strong>field</strong> geologist. It allows<br />
him now to "think out <strong>of</strong> the box" and not be tied to models that are not quite his<br />
deposit type. Portable spectrometers at the outcrop, in the core shack, in the<br />
open pit, give the explorationist instant information about rocks that may all have<br />
similar physical appearances. Portable spectrometers provide in-situ data that<br />
allows the geologist to immediately integrate several data sets - geophysics,<br />
geochemistry and mineralogy - in the <strong>field</strong> - at the outcrop, where this information<br />
can be quickly applied to a better understanding <strong>of</strong> what is physically observed -<br />
instant gratification. This was not possible before their invention. Reflectance<br />
<strong>spectroscopy</strong> is changing the nomenclature <strong>of</strong> exploration and allowing<br />
geologists to look at mineral associations that provide more in depth<br />
understanding <strong>of</strong> not only the rocks themselves, but the processes that have<br />
altered them into the precious metal resources so important to the world.<br />
This paper will therefore present an <strong>overview</strong> <strong>of</strong> <strong>vis</strong>ible through SWIR (Short<br />
Wave Infrared) <strong>field</strong> <strong>spectroscopy</strong> with a brief summary <strong>of</strong> theory and<br />
applications. Emphasis is placed on alteration systems, especially those<br />
associated with low and high sulfidation gold deposits, porphyries, kimberlites,<br />
skarns, IOCG (iron oxide copper gold) and unconformity uranium deposits, all <strong>of</strong><br />
which are major successes for reflectance <strong>spectroscopy</strong>.<br />
Introduction -<br />
Many innovations have occurred in exploration and mining that have contributed<br />
to assisting the industry to find more precious metals resource and to find it<br />
faster. One such innovative technology is that <strong>of</strong> VIS-NIR-SWIR (Visible – Near-<br />
Infrared - Short-wave Infrared) reflectance <strong>spectroscopy</strong>. Its use has caused<br />
major changes in the way exploration is done and how explorationists think as<br />
now they are provided with instant information about the minerals in their rocks.<br />
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The utilization <strong>of</strong> this range (350 to 2500nm) <strong>of</strong> the Electromagnetic Spectrum for<br />
mineral exploration comes out <strong>of</strong> remote sensing needs as does the invention<br />
and subsequent refinements <strong>of</strong> the <strong>field</strong> spectrometers, which have become the<br />
prime vehicles for this methodology. Initial <strong>field</strong> units from the GER Mark series<br />
(Geophysical Environmental Resources <strong>of</strong> Millbrook New York) to the ASD<br />
classics and FieldSpec Pros were developed using solar illumination to<br />
correspond to the satellite and airborne sensors for which they provided ground<br />
truth or verification.<br />
With the addition <strong>of</strong> an internal light source to eliminate the effects <strong>of</strong><br />
atmospheric water spectra, users quickly discovered that the portable<br />
spectrometers had so many more applications then just ground truthing remotely<br />
sensed data and the technology came into its own.<br />
Although there are numerous companies <strong>of</strong>fering instruments in the Visible and<br />
short wave infrared for applications ranging from vegetation, water, forestry,<br />
wood products, paint, carpets, wheat protein content, pharmaceuticals, forensics,<br />
plastics, oil, among others, most are not portable to the <strong>field</strong> nor general enough<br />
for geologic applications. GER was the company with the Mark series <strong>of</strong> <strong>field</strong><br />
spectrometers, who has always been more involved in the general remote<br />
sensing side <strong>of</strong> the application rather then specifically targeting the mining<br />
industry. Alex Goetz, at that time <strong>of</strong> Jet Propulsion Laboratory, Ron Lyon <strong>of</strong><br />
Stanford University, Larry Rowan <strong>of</strong> the U.S. Geological Survey, Robert Agar <strong>of</strong><br />
AGARS, Australia, Jon Huntington, CSIRO, Australia, Fred Kruse <strong>of</strong> AIG, Floyd<br />
Sabins <strong>of</strong> Chevron, Jim Taranik <strong>of</strong> the University <strong>of</strong> Nevada-Reno, and the<br />
present author, among hundreds <strong>of</strong> others, have all used this instrument for<br />
mostly geologic, but some exploration and mining, applications. At issue has<br />
always been the solar illumination and the corresponding atmospheric water<br />
interference bands that mask out vital components and absorption features in the<br />
mineral spectra. This interference made the application less attractive for<br />
alteration characterization. Even 15 years ago, the solar illumination-based<br />
technology was the best available.<br />
With the introduction <strong>of</strong> the internal light source, the PIMA-II <strong>field</strong> spectrometer by<br />
Integrated Spectronics <strong>of</strong> Sydney, Australia, in the early 1990s, the concept <strong>of</strong><br />
portability and <strong>field</strong> characterization <strong>of</strong> alteration took on a new perspective and<br />
many new applications. Over 200 PIMAs, the majority <strong>of</strong> which are still<br />
operational, were pioneering devices for developing new methods <strong>of</strong> alteration<br />
mapping, core logging, drill well targeting, and <strong>field</strong> reconnaissance. Most <strong>of</strong> the<br />
major mining companies worldwide adopted this new technology and utilized it<br />
well for new discoveries and in-depth knowledge <strong>of</strong> their alteration systems.<br />
In the late 1990s, ASD Inc. (formerly <strong>An</strong>alytical <strong>Spectral</strong> Devices, Inc.)<br />
introduced their FieldSpec Pro. This instrument did have an internal light<br />
source probe on it. It was upgraded in 2005 to the “FR3”, which had a refined<br />
probe. Neither <strong>of</strong> these instruments were designed for the minerals industry, but<br />
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were designed more for general remote sensing with solar illumination as the<br />
prime light source. It was the appearance <strong>of</strong> the ASD TerraSpec in 2004 with<br />
its flexible and innovative design specifically for minerals and mining that has<br />
brought cutting edge, fast, fiber-optic data collection into the <strong>field</strong> and core shack.<br />
This paper will review the concepts <strong>of</strong> reflectance <strong>spectroscopy</strong>, and look at the<br />
more practical information that can be obtained from the <strong>vis</strong>ible, near-infrared,<br />
and short-wave infrared regions <strong>of</strong> spectra, beyond just simple mineral<br />
identification. Routine applications such as core logging, <strong>field</strong> reconnaissance,<br />
pit mapping, and remote sensing ground truth will be illustrated with examples.<br />
Selected alteration systems for gold, porphyries, diamonds, unconformity<br />
uranium, IOCGs and skarns will be summarized from a spectral perspective and<br />
mini-case studies discussed, space permitting.<br />
REFLECTANCE SPECTROSCOPY<br />
Spectroscopy is the study <strong>of</strong> the interaction between energy as electromagnetic<br />
radiation (EMR) and matter. Radiation can be absorbed, emitted or scattered by<br />
matter.<br />
Reflectance <strong>spectroscopy</strong> can be defined as the technique that uses the energy<br />
in the Visible (0.4-0.7), Near-Infrared (0.7-1.0) and Short-Wave Infrared (1.0-2.5<br />
µm) wavelength regions <strong>of</strong> the electromagnetic spectrum (Figure 1) to analyze<br />
minerals.<br />
Figure 1. – Highly generalized cartoon <strong>of</strong> the EMS showing the various regions that<br />
are covered by <strong>field</strong> portable spectrometers. Source unknown.<br />
The science and techniques <strong>of</strong> reflectance <strong>spectroscopy</strong> are based on the<br />
spectral properties <strong>of</strong> materials. Certain atoms and molecules absorb energy as<br />
a function <strong>of</strong> their atomic structures. (Hunt, 1977 and Goetz et al, 1982).<br />
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In the <strong>vis</strong>ible region, this is caused by electronic transitions such as Crystal Field<br />
Effects (atomic energy level transitions), Charge Transfer (inter-element<br />
electronic transitions), Conduction Band Transitions (electron transfer over<br />
spatially close energy levels) and Color Center Phenomenon (lattice defect<br />
induced energy levels). . Much <strong>of</strong> this simply involves release <strong>of</strong> energy when an<br />
electron changes energy levels in an atom.<br />
Absorption features in the SWIR region are a function <strong>of</strong> the composition <strong>of</strong> the<br />
mineral. They are a manifestation <strong>of</strong> energy absorption within the crystal lattice<br />
from vibrational state transitions. Because these vibrational states correspond to<br />
distinct energy levels, the absorption features occur at well-defined wavelength<br />
positions. The energy levels that define these wavelengths are a function <strong>of</strong> the<br />
size <strong>of</strong> the ionic radii <strong>of</strong> the cations bonded to different molecules. The bonds will<br />
vibrate at different wavelengths as a function <strong>of</strong> the length <strong>of</strong> the bond. Because<br />
the bond lengths between a specific atom and molecule will be consistent, it is<br />
possible to predict compositions and compositional changes in minerals being<br />
analyzed by the wavelengths and wavelength shifts. (Hunt, 1977)<br />
The transitions between energy levels and compositional differences are<br />
manifested by absorption features at defined wavelengths. The common<br />
absorption feature positions are listed in Table I.<br />
TABLE I – MAJOR ABSORPTION FEATURES<br />
POSITION MECHANISM MINERAL GROUP<br />
~1.4 µm OH and WATER CLAYS, SULFATES<br />
HYDROXIDES,<br />
ZEOLITES<br />
~1.56 µm NH4 NH4 SPECIES<br />
~1.,8 µm OH SULFATES<br />
~1.9 µm WATER SMECTITE<br />
2.02, 2.12 µm NH4 NH4 SPECIES<br />
~2.2 µm AL-OH CLAYS,.<br />
SULFATES, MICAS<br />
~2.29 Fe-OH Fe-CLAYS<br />
~2.31 Mg-OH Mg-CLAYS,<br />
ORGANICS<br />
~2.324 Mg-OH CHLORITES<br />
-2<br />
~2.35 +/- µm CO3<br />
CARBONATES<br />
~2.35+ Fe-OH Fe-CHLORITES<br />
The absorption features occur within a reflectance spectrum, with wavelength<br />
positions and distinctive pr<strong>of</strong>iles that can be used to identify mineral and organic<br />
phases. These are shown in Figure 2 below.<br />
Each mineral has a distinctive spectral signature, composed <strong>of</strong> several<br />
absorption features, which is a function <strong>of</strong> composition, crystallinity,<br />
5
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concentration, water content and environmental considerations. For mineral<br />
identification, that signature is compared against characterized references for a<br />
validated identification. This can be done manually by using wavelength tables<br />
and overlaying references on the unknown or it can be done using computer<br />
algorithms operating against a database <strong>of</strong> references (i.e., a spectral library).<br />
For best results these libraries must be set up for specific deposit types, and not<br />
allow the algorithm to make a wrong choice.<br />
Figure 2 – Example absorption spectrum. The units for the horizontal scale are in<br />
nanometers or microns while the vertical scale is percent reflectance. The absorption<br />
figure shown is a doublet, with two minima or lowest points <strong>of</strong> the feature. Each<br />
minimum has a distinctive wavelength, which is a function <strong>of</strong> the chemical<br />
composition. “FWHM” means Full Width at Half Maximum. It can be used for<br />
symmetry determinations that are related to crystallinity.<br />
Although the computer algorithms are useful for data management and<br />
organization, care must be taken when using them for phase identification and<br />
quantification. There are many unaddressed variables and non-user chosen<br />
identifications are not always accurate. Additionally, important information on<br />
crystallinity, water, organics, and iron, among other things, is lost.<br />
VISIBLE RANGE SIGNATURES<br />
There is an abundance <strong>of</strong> information to be gained from the <strong>vis</strong>ible region <strong>of</strong> the<br />
EMS. This is one <strong>of</strong> the features that makes the full-range spectrometers so<br />
valuable. Figure 3 shows some <strong>of</strong> the cations that are recognizable by colors<br />
and corresponding minerals. Although the <strong>vis</strong>ible range is constrained from 300-<br />
6
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720nm, there is additional and complimentary information in the NIR (700 nm to<br />
1000 nm).<br />
Figure 3. – The plot shows some <strong>of</strong> the more common cations that can be identified in<br />
the <strong>vis</strong>ible range.<br />
For example, chlorites are more detectable in the <strong>vis</strong>ible range because there is<br />
less interference from other species compared to in the SWIR range where their<br />
signal is usually low unless chlorites are the dominant phase. Iron oxyhydroxides<br />
(Figure 4) have many distinctive features that allow them to be discriminated<br />
from each other. This allows a discrimination <strong>of</strong> pH zoning and something not<br />
easily done before. The nickel cation also has diagnostic features in the <strong>vis</strong>ible<br />
range that can be detected in nickel laterite deposits and correlated to the ore<br />
zones. Chrome in kimberlite minerals such as chrome diopside and G-10<br />
garnets make <strong>spectroscopy</strong> invaluable to the identification <strong>of</strong> indicator minerals.<br />
Manganese is also detectable through features in the <strong>vis</strong>ible range.<br />
Garnets, pyroxenes, olivine, selected iron and copper oxides, hydroxides,<br />
sulfates, and for heavy element carbonates, a NIR major absorption feature.<br />
7<br />
Fe2+ Fe2+ chlorites<br />
Fe3+ hematite, goethite<br />
Ni Chrysoprase<br />
Cr Cr-diopside<br />
Mn Mn-chlorite<br />
Mn rhodonite<br />
Mn rhodocrosite
________________________________________________________________<br />
A<br />
USGS References<br />
Figure 4 – The plots in [A] show the classic three most common iron minerals encountered in<br />
exploration; jarosite, hematite and goethite. Stronger acidic minerals are shown in [B]. These<br />
include, from top to bottom, schwertmannite, jarosite, copiapite, coquimbite and melanterite.<br />
Rare Earth elements (REE) have<br />
very distinctive signatures in the<br />
<strong>vis</strong>ible region as can be seen in<br />
Figure 5. Rare Earth minerals<br />
include such species as bastnesite<br />
(CeFCO 3 ), monzonite (Ce, La,Y,Th)<br />
PO 4 , and xenotime (YPO 4 ). The<br />
two most famous REE mines in the<br />
world are located at Mountain Pass,<br />
California and Bayan Obo, China.<br />
8<br />
SPECMIN References<br />
B<br />
Figure 5 – Plots <strong>of</strong> europium, neodymium oxide,<br />
samarium oxide, praseodymium oxide from the<br />
USGS reference library.
________________________________________________________________<br />
SWIR RANGE SIGNATURES<br />
The <strong>field</strong> spectrometers are probably the best tools invented in the last 10 years,<br />
aside from GPS, for <strong>field</strong> reconnaissance and core logging. They can be taken<br />
to the <strong>field</strong>, to the pit and to the outcrops. They operate from a backpack or from<br />
the <strong>field</strong> vehicle. They can be set up in a <strong>field</strong> camp, in a core shack, or on an<br />
outcrop. They are versatile and flexible and provide the explorationist with “on<br />
the spot”, in-situ information, right at the outcrop, so there is instant gratification<br />
and instant knowledge <strong>of</strong> the composition <strong>of</strong> the outcrop or the drill core.<br />
Alteration types are instantly identified, mixtures are seen, zoning can be tracked,<br />
mineral transition zones characterized. Ten years ago, this was just becoming a<br />
possibility. Now it can be done in a tenth <strong>of</strong> a second.<br />
What can be seen? Table II, from Thompson and Thompson (1996) summarizes<br />
the majority <strong>of</strong> the common infrared-active minerals that can be detected in the<br />
SWIR range.<br />
Table II – Summary <strong>of</strong> Infrared Active Minerals with SWIR Absorption Features<br />
Environment <strong>of</strong> formation Standard terminology SWIR active mineral assemblage (key minerals are in bold)<br />
Intrusion-related<br />
High-sulfidation epithermal<br />
Low-sulfidation epithermal<br />
Mesothermal<br />
Potassic (biotite-rich), K silicate,<br />
biotitic<br />
Biotite (phlogopite), actinolite, sericite, chlorite, epidote,<br />
muscovite, anhydrite<br />
Sodic, sodic-calcic Actinolite, clinopyroxene (diopside), chlorite, epidote, scapolite<br />
Phyllic, sericitic Sericite (muscovite-illite), chlorite, anhydrite<br />
Intermediate argillic, sericite-<br />
chlorite-clay (SCC), argillic<br />
Sericite (illite-smectite), chlorite, kaolinite (dickite),<br />
montmorillonite, calcite, epidote<br />
Advanced argillic Pyrophyllite, sericite, diaspore, alunite, topaz, tourmaline,<br />
dumortierite, zunyite<br />
Greisen Topaz, muscovite, tourmaline<br />
Skarn Clinopyroxene, wollastonite, actinolite-tremolite, vesuvianite, epidote,<br />
serpentinite-talc, calcite, chlorite, illite-smectite, nontronite<br />
Propylitic Chlorite, epidote, calcite, actinolite, sericite, clay<br />
Advanced argillic — acid sulphate Kaolinite, dickite, alunite, diaspore, pyrophyllite, zunyite<br />
Argillic, intermediate argillic Kaolinite, dickite, montmorillonite, illite-smectite<br />
Propylitic Calcite, chlorite, epidote, sericite, clay<br />
“Adularia” — sericite, sericitic,<br />
argillic<br />
Advanced argillic —<br />
acid-sulphate (steam-heated)<br />
Sericite, illite-smectite, kaolinite, chalcedony, opal,<br />
montmorillonite, calcite, dolomite<br />
Kaolinite, alunite, cristobalite<br />
(opal, chalcedony), jarosite<br />
Propylitic, zeolitic Calcite, epidote, wairakite, chlorite,<br />
illite-smectite, montmorillonite<br />
Carbonate Calcite, ankerite, dolomite, muscovite (Cr-/V-rich), chlorite<br />
Chloritic Chlorite, muscovite, actinolite<br />
Biotitic Biotite, chlorite<br />
Sediment-hosted gold Argillic Kaolinite, dickite, illite<br />
Volcanogenic massive sulfide<br />
Sediment-hosted massive sulfide<br />
Sericitic Sericite, chlorite, chloritoid<br />
Chloritic Chlorite, sericite, biotite<br />
Carbonate Dolomite, siderite, ankerite, calcite, sericite, chlorite<br />
Tourmalinite Tourmaline, muscovite<br />
Carbonate <strong>An</strong>kerite, siderite, calcite, muscovite<br />
Sericitic Sericite, chlorite<br />
Albitic Chlorite, muscovite, biotite<br />
Minerals are grouped by assemblages <strong>of</strong> alteration minerals, and keyed to commonly used terminology; Complete assemblages are in<br />
Thompson and Thompson (1996)<br />
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The SWIR method does not detect minerals per se, but the vibrational energy <strong>of</strong><br />
the chemical bonds between atom and molecule in the octahedral layer <strong>of</strong> a<br />
compound. This gives more flexibility in detecting amorphous materials.<br />
Therefore, it is possible to detect Si-OH bonds and thus look at amorphous<br />
silicas, such as opaline phases.<br />
SWIR is also very sensitive to water, which will be illustrated in a later section.<br />
This is particularly valuable when tracking fluid migration through a deposit.<br />
The common molecules detected are H2O, OH, CO3, and NH4. Selected sulfates<br />
are seen when an OH bond is present, as are phosphates (Figure 6). Table II<br />
lists most <strong>of</strong> the common infrared-active<br />
minerals. The groups most likely<br />
encountered, with selected mineral<br />
examples, include clays (illite,<br />
illite/smectite, kaolinite, smectites,<br />
dickite) and all pyllosilicates, carbonates<br />
(calcite, dolomite, ankerite, siderite,<br />
malachite, azurite, cerrusite), micas<br />
(muscovite, biotite, phlogopite,<br />
paragonite), chlorites (Mg, Fe, Al),<br />
Sulfates (alunite, jarosite, gypsum, Fesulfates),<br />
tourmaline (schorl, elbaite,<br />
dravite, rubellite), amphiboles (tremolite,<br />
actinolite, hornblende), pyroxenes<br />
(diopside, augite, hypersthene), garnets<br />
(pyrope, almandine, grossularite),<br />
pyroxinoids (rhodonite, sodalite)<br />
selected silicates (talc, topaz, scapolite,<br />
pyrophyllite, zunyite, epidote, olivine,<br />
serpentines, dumortierite , idocrase)<br />
evaporates (sulfates, niter, anhydrite,<br />
gypsum, borax minerals),hydroxides<br />
(diaspore, brucite), zeolites (stilbite,<br />
heulendite, clinoptilolite), and silica<br />
(opal, quartz, sinter)<br />
pl<br />
Figure 6. – These are plots <strong>of</strong><br />
common alteration minerals.<br />
(Thompson et al, 1999).<br />
Limits <strong>of</strong> detection will vary with the<br />
matrix composition and the active versus<br />
inactive components. It varies between<br />
mineral mixtures. It is very difficult to do<br />
accurate quantitative mixtures without first<br />
building calibration files <strong>of</strong> percentage<br />
mixtures.<br />
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SPECTRAL INFORMATION<br />
Field Spectrometers, whether they are based on an integrating sphere or fiber<br />
optic cable, allow the collection and presentation <strong>of</strong> spectral data. Although the<br />
primary objective <strong>of</strong> this operation is the identification <strong>of</strong> the minerals found in<br />
different alteration systems, there is other information that can be obtained from<br />
the data and which is <strong>of</strong> great significance in the interpretation <strong>of</strong> the spectral<br />
information. These include chemical substitution, crystallinity, effects <strong>of</strong> water,<br />
paragenesis and temperature.<br />
CHEMISTRY<br />
The ability to discern compositional differences in mineral groups that have solid<br />
solution substitution is very useful. Some examples are the carbonates,<br />
amphiboles, chlorites, illite/micas, tourmalines, smectite clays, alunites, all <strong>of</strong><br />
which exhibit wavelength shifts with cation substitution (Figure 7A, 7B, and 7C).<br />
A B<br />
Figure 7 – The spectral plots in [A] are for alunites <strong>of</strong> different compositions from Ca to Na<br />
to K to NH4. Note that the diagnostic feature ranges from 1495nm for Ca to 1460nm for<br />
NH4 . In Figure 7B, the diagnostic wavelength shift occurs in the 2330 nm range for Mgchlorites<br />
shifting to 2350+ for Fe-chlorites. The carbonate group is shown in [C]. These<br />
mineral show a significant shift with different cation compositions ranging from (top to<br />
bottom) aragonite (Ca), Dolomite (Mg, Ca), calcite (Ca), rhodocrosite (Mg), stronianite (Sr),<br />
magnesite (Mg), cerrusite (Pb), siderite (Fe), ankerite (fe, Mg), malachite (Cu), and azurite<br />
(Cu).<br />
11<br />
C
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IRON OXYHYDROXIDES AND SULFATES<br />
Iron oxides, hydroxides, oxyhydroxides and sulfates are very important not only<br />
to precious metals exploration, but also in the determination <strong>of</strong> oxidation states<br />
and acid drainage creation potential. They can be used in the <strong>field</strong> to provide<br />
approximate pH's in an environment, especially along a stream, as shown in the<br />
cartoon below. The three most common iron minerals are plotted in Figure 9.<br />
PYRITE<br />
SOURCE<br />
SPRING<br />
PH = 2.3-2.8<br />
JAROSITE<br />
KFe III (SO4)(OH)6<br />
melanterite<br />
copiapite<br />
Bigham et al, 1996<br />
pH = 3<br />
pH = 4<br />
SCHWERTMANNITE<br />
Figure 8 - This cartoon shows pH changes along a stream from a sulfide metals source through<br />
neutralization <strong>of</strong> acid waters by dilution and volume effects.<br />
703<br />
Fe8 III O8(SO4)(OH)6<br />
745<br />
766<br />
862<br />
894<br />
920<br />
Source: US Geological Survey data base.<br />
pH = 4<br />
12<br />
No jarosite<br />
FERRIHYDRITE<br />
~Fe3O8.4H2O<br />
pH = 6<br />
pH = 7<br />
STREAM<br />
GOETHITE<br />
α = FeOOH<br />
Lepidocrocite<br />
Maghemite<br />
Figure 9 - The three most<br />
common iron minerals<br />
encountered in gold and copper<br />
deposits are jarosite, goethite<br />
and hematite. The plot shows<br />
spectral pr<strong>of</strong>iles and<br />
wavelengths for these minerals<br />
in the <strong>vis</strong>ible range, where most<br />
<strong>of</strong> their diagnostic features<br />
occur. The emission features<br />
are more consistent and<br />
reproducible then the<br />
absorption features. These<br />
features all have a range.<br />
These minerals are usually<br />
mixtures <strong>of</strong> each other and<br />
therefore a wavelength range is<br />
more applicable to defining<br />
them.
435<br />
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430<br />
430<br />
468<br />
430<br />
B<br />
560<br />
518<br />
IRON OXIDES OXYHYDROXIDES<br />
795<br />
782<br />
769<br />
761<br />
748<br />
920<br />
855<br />
961<br />
922<br />
959<br />
ACID IRON SULFATES<br />
733<br />
682<br />
655<br />
713<br />
776<br />
874<br />
871<br />
917<br />
927<br />
A<br />
Lepidocrocite<br />
Ferrihydrite<br />
Maghemite<br />
Goethit<br />
Hematite<br />
Schwertmannite<br />
Jarosite<br />
Copiapite<br />
Coquimbite<br />
Melanterite<br />
13<br />
Figure 10 - For most <strong>of</strong> these iron<br />
species, the definitive features are<br />
found in the <strong>vis</strong>ible region. The more<br />
common iron oxides and hydroxides are<br />
plotted in Figure 10A and include<br />
lepidocrocite, ferrihydrite, maghemite.<br />
Goethite and hematite.<br />
The iron sulfates are very useful for help<br />
in determining pH <strong>of</strong> their environment<br />
and potential acid drainage factors.<br />
They are plotted in Figures 10B for<br />
Visible range and 10C for SWIR range<br />
and include schwertmannite, jarosite,<br />
copiapite, coquimbite and melanterite.<br />
Except for jarosite, they show mostly<br />
water features in the SWIR. A full range<br />
spectrometer is therefore essential for<br />
their definitive identification.<br />
C<br />
Schwertmannite<br />
Jarosite<br />
Copiapite<br />
Coquimbite<br />
Melanterite
________________________________________________________________<br />
<strong>An</strong>other perspective <strong>of</strong> this shift is the aluminum substitution in illites and Al-micas.<br />
Figure 11- Aluminum content <strong>of</strong> illites can be<br />
estimated from the 2.2 µm absorption<br />
feature, which shifts relative to the percent<br />
aluminum present. There appears to be a<br />
deposit-specific correlation in that when<br />
illite/”sericite”/muscovite alteration is present,<br />
there are higher amounts <strong>of</strong> aluminum<br />
apparently associated with the ore zones.<br />
This also has been documented by Post and<br />
Noble (1993) and their data is plotted below<br />
against spectral wavelength values collected<br />
from their published samples.<br />
Figure 13 – Selected Georgia kaolinites,<br />
showing decreasing crystallinity down the<br />
plot. Crystallinity index is based on work<br />
done by Murray and Lyons (1956). Note<br />
how water content increases with<br />
decreasing crystallinity.<br />
14<br />
Figure 12- Feature positions for a cross section<br />
<strong>of</strong> muscovites and illites from SPECMIN range<br />
from 2198nm to 2212 nm, with the majority falling<br />
within 2200-2204 nm.<br />
The illites plotted in Figure 9 are from different<br />
environments and from top to bottom are [A] Hog<br />
Ranch, Nevada, epithermal gold deposit; [B]<br />
Chuquicamata, Chile, porphyry copper; [C]<br />
Leadville, Colorado, gold vein system; [D]<br />
Cananea, Mexico, porphyry copper deposit; [E]<br />
Round Mountain, Nevada, disseminated gold<br />
deposit; [F, G, H] sedimentary illites from Illinois<br />
shales.<br />
Degree <strong>of</strong> crystallinity can be determined<br />
from change in the pr<strong>of</strong>ile, using a<br />
calibration data set for comparison<br />
(Figure 13 ).<br />
Note how the kaolinite doublet in the<br />
2200 nm region s<strong>of</strong>tens and broadens<br />
from a sharp, well-defined minimum to a<br />
shoulder as ordering decreases.<br />
This change in pr<strong>of</strong>ile can be<br />
mathematically defined and utilized as an<br />
index. It is a function <strong>of</strong> random and<br />
sporadic filling <strong>of</strong> metal sites in the<br />
octahedral layer <strong>of</strong> the mineral. Empty<br />
and random sites decrease order and,<br />
therefore, the sharpness <strong>of</strong> the pr<strong>of</strong>ile.
________________________________________________________________<br />
PARAGENESIS AND WATER<br />
Pr<strong>of</strong>iles also give information related to paragenesis and, indirectly, temperature<br />
(Figure 15). Broad, open absorption features coupled with large water features<br />
such as those found in smectites, zeolites, and opaline silica minerals indicate<br />
ambient to low temperatures from low energy environments. As the pr<strong>of</strong>ile<br />
sharpens and becomes well defined, such as in muscovites, pyrophyllite,<br />
epidote, and dickite, the temperature <strong>of</strong> formation increases and the crystal<br />
lattice becomes ordered in a high-energy environment.<br />
Figure 15 - plots showing changes in pr<strong>of</strong>ile<br />
As a function <strong>of</strong> ordering in the crystal lattice,<br />
From broad, low temperature smectites to<br />
higher temperature mica and pyrophyllite.<br />
15<br />
Figure 14 - A very important series is the<br />
one from montmorillonite (A) through to<br />
muscovite [I]. This goes through mixed<br />
layer smectite/illite [B] and illite/smectite<br />
[C, D] to illite [E, F, G, H]. The plot<br />
summaries the species in this series and<br />
shows the information that can be gained<br />
by the wavelength shift indicating<br />
changes in aluminum content. This is<br />
the most complicated series commonly<br />
worked with in alteration systems.<br />
Changes in water content, pr<strong>of</strong>ile shape<br />
and wavelength are all subtle between<br />
the different species in the series. They<br />
are difficult to distinguish and can only<br />
be differentiated by comparison against<br />
references.<br />
Figure 16 - plots different water sites from<br />
channel water in beryl to molecular water<br />
in gypsum to zeolite channel water to<br />
interlayer water in smectite to surface<br />
water.
________________________________________________________________<br />
Type <strong>of</strong> water present also can be tracked relative to pr<strong>of</strong>ile and wavelength<br />
(Figure 16). As seen in the figure, different types <strong>of</strong> water (channel, structural,<br />
interlayer, surface, silica, encapsulated), have different pr<strong>of</strong>iles which provide<br />
information about how the water was formed and where it resides.<br />
II. DATA COLLECTION AND ANALYSIS Applications Examples<br />
Outcrop mapping - Pamel<br />
Pamel: <strong>An</strong> alteration study <strong>of</strong> the Pamel prospect in the Western Cordillera<br />
<strong>of</strong> Peru was conducted for Candente Resource Corp. The results from<br />
approximately 12 samples were integrated with geologic information and<br />
outcrop patterns. Based on 3 days work, combined with the previous<br />
geologic data, an alteration map was created for the property. The results<br />
clearly showed distinct alteration zones and helped delineate zones <strong>of</strong><br />
interest (Figure 17). The alteration varies, from silicification to alunite-dickite,<br />
to alunite-kaolinite, to kaolinite dominant, and outward to sericite, illite,<br />
and chlorite. Small amounts <strong>of</strong> diaspore, topaz, and tourmaline were also<br />
noted locally (Thompson et al., 1999).<br />
Figure 17. - alteration map created by A. Thompson from PIMA outcrop samples.<br />
16
________________________________________________________________<br />
Core Logging<br />
<strong>Spectral</strong> core logging is one <strong>of</strong> the major applications <strong>of</strong> reflectance<br />
<strong>spectroscopy</strong>. Figure 18 presents a spectral core log..<br />
HIGH SULFIDATION SYSTEM DRILL HOLE :: GOLD vs MINERALOGY<br />
DEPTH Wave Au Kl Dik Alk Ill Sm Sil Jar Ch ALT Minerals<br />
40 2206 0.005 x x 1 Jarosite, trace gyp, illite?<br />
68 2206 0.005 x x 1 Illite + silica<br />
74 2206 0.009 tr x x 1 Illite, silica tr gyp tr kaolinite<br />
80 2206 0.024 x x x 1 Illite -> kaolinite, gyp, silica<br />
81 2204 0.024 x x 1 Illite, gypsum - - jarosite?<br />
94 2210 0.007 x 1 Illite<br />
100a 2206 0.013 x x 1 Illite, jarosite<br />
117 2206 0.008 x 1 Illite<br />
124 2204 0.025 x x 1 Illite jarosite<br />
140 2212 0.005 x x 1 Illite, jarosite, gypsum?<br />
146 2192 0.011 x x 1 Illite, silica<br />
150 2164 0.011 x 1 Kaolinite<br />
164 2166 0.099 x 1 Kaolinite, well x/n<br />
170 2168 0.099 x 1 Kaolinite, MW<br />
173 2180 1.473 x x x 4 Dickite, alunite, kaolinite<br />
175 2180 1.473 x x 4 Alunite + dickite<br />
178 2170 1.473 x x 5 Alunite + silica<br />
181 2177 0.133 x x x 4 Dickite and alunite silica<br />
182 2181 0.133 x tr 3 Dickite, trace alunite<br />
183 2180 0.133 x 3 Dickite<br />
186 2166 0.035 x 1 Best kaolinite<br />
196 2167 0.013 x x 1 Kaolinite + silica<br />
204 2167 0.005 x 1 Kaolinite<br />
214 2177 0.099 x tr 1 Kaolinite tr dickite<br />
218 2166 0.099 x x 1 Kaolinite - poor illite<br />
224 2166 0.016 tr x 1 Smectite + minor kaolinite<br />
229 2167 0.016 x 1 Kaolinite<br />
235 2164 0.196 x 1 Kaolinite - still wet<br />
238 2164 0.196 x 1 Kaolinite<br />
244 2164 0.007 x 1 Kaolinite<br />
Pit Bench Mapping - Blast Holes<br />
Considerable information can be gained through the analysis <strong>of</strong> blast holes in an<br />
open pit mine. Although blast holes are assayed, in-situ mineralogical analysis<br />
can provide alteration types, which if spectrally defined, will give the metallurgist<br />
information needed for efficient mill recovery or heap leach pad blending.<br />
17<br />
A<br />
B<br />
C<br />
D<br />
E<br />
F<br />
Figure 18 - <strong>An</strong> Excel chart<br />
that shows mineralogy<br />
against alteration type<br />
against gold assay values.<br />
Plotting the minerals in this<br />
way gives an excellent<br />
comparison <strong>of</strong> the<br />
presence <strong>of</strong> gold related to<br />
mineralogy. The alteration<br />
classifications are<br />
indigenous to the high<br />
sulfidation system and<br />
represent mineral<br />
associations.<br />
Figure 19 - This plot is a compilation <strong>of</strong><br />
different alteration types from a copper<br />
mine, defined using <strong>spectroscopy</strong>.<br />
These include [A] muscovite, [B]<br />
weathered muscovite shown by large<br />
water feature, [C] illite with very minor<br />
kaolinite overprint, [D] illite - kaolinite<br />
mixture, [E] kaolinite – illite mixture, [F]<br />
kaolinite. By matching metallurgical<br />
data to the clay type, it was possible to<br />
determine that too much kaolinite<br />
would cause recovery losses.
________________________________________________________________<br />
ALTERATION SYSTEMS FROM THE SPECTRAL PERSPECTIVE<br />
The more common deposits that can be defined by reflectance <strong>spectroscopy</strong><br />
include epithermal gold, low and high sulfidation systems; porphyries,<br />
kimberlites, IOCG (Iron Oxide-Copper-Gold), skarns, and uranium (both<br />
sandstone hosted sediment and unconformity types). Although there are<br />
numerous other deposit and alteration types that can be analyzed successfully<br />
with this method, space constraints allow only an <strong>overview</strong> <strong>of</strong> the above list.<br />
This section therefore presents a very brief definition <strong>of</strong> the deposit type,<br />
reference to a graphic model, list the better-known deposit examples, and<br />
discuss the alteration from the spectral perspective. The information presented<br />
here as background to the deposit type and alteration systems has been<br />
compiled from references and from websites.<br />
Definition <strong>of</strong> deposit type<br />
EPITHERMAL GOLD - LOW SULFIDATION<br />
Epithermal gold deposits form in hydrothermal systems related to volcanic<br />
activity. These systems, while active, discharge to the surface as hot springs or<br />
fumaroles. Epithermal gold deposits occur largely in volcano-plutonic arcs<br />
(island arcs as well as continental arcs) associated with subduction zones, with<br />
ages similar to those <strong>of</strong> volcanism. The deposits form at shallow depth,
________________________________________________________________<br />
Boiling <strong>of</strong> liquid in the LS geothermal environment leads to precipitation <strong>of</strong> gold<br />
in veins accompanied by a variety <strong>of</strong> features such as adularia and bladed<br />
calcite cementing coll<strong>of</strong>orm and brecciated quartz. Silica sinters may be the<br />
surface expression <strong>of</strong> such veins and may be accompanied by nearby zones <strong>of</strong><br />
surficial steam-heated acid alteration<br />
These deposits form in both subaerial, predominantly felsic, volcanic <strong>field</strong>s in<br />
extensional and strike-slip structural regimes and island arc or continental<br />
andesitic stratovolcanoes above active subduction zones. Near-surface<br />
hydrothermal systems, ranging from hot springs at surface to deeper, structurally<br />
and permeability focused fluid flow zones are the sites <strong>of</strong> mineralization. The ore<br />
fluids are relatively dilute and cool solutions that are mixtures <strong>of</strong> magmatic and<br />
meteoric fluids. Mineral deposition takes place as the solutions undergo cooling<br />
and degassing by fluid mixing, boiling, and decompression.<br />
http://www.em.gov.bc.ca/mining/Geolsurv/MetallicMinerals/MineralDepositPr<strong>of</strong>ile<br />
s/pr<strong>of</strong>iles/h05.htm Panteleyev (1996):<br />
Model for Low Sulfidation Epithermal Vein Systems<br />
Figure 20 - Figure shows a model for a low-sulfidation epithermal gold system. Note distribution<br />
<strong>of</strong> alteration zoning and know deposits. (Corbett and Leach, 1998)<br />
19
________________________________________________________________<br />
Major Global Deposits<br />
EL PEÑON, Chile MARTA, Peru<br />
ESQUEL, Argentina ROUND MOUNTAIN, Nevada<br />
CERRO VANGUARDIA, Argentina COMSTOCK, Virginia City, Nevada<br />
HISHIKARI, Japan SLEEPER, Nevada<br />
GOSAWONG , Indonesia MIDAS, Nevada<br />
KUPOL, Russia WAIHI , New Zealand<br />
ROSIA MONTANA, Romania GOLDEN CROSS, New Zealand<br />
LIHIR, PNG CERRO BAYO, Chile<br />
TRES CRUCES, Peru KORI KOLLO, Bolivia<br />
COMMON ALTERATION MINERALS in LOW SULFIDATION SYSTEMS<br />
ILLITE KAOLINITE CHLORITES<br />
ILLITE/SMECTITE BUDDINGTONITE EPIDOTE<br />
Montmorillonite ADULARIA* ZEOLITES<br />
QUARTZ CALCITE HEMATITE<br />
*Adularia is not infrared active.<br />
Alteration types associated with Low Sulfidation Systems<br />
Silicification is extensive in ores as multiple generations <strong>of</strong> quartz and<br />
chalcedony and commonly is accompanied by adularia and calcite. Pervasive<br />
silicification in vein envelopes is flanked by sericite-illite-kaolinite assemblages.<br />
Intermediate argillic alteration [kaolinite-illite-montmorillonite (smectite)] forms<br />
adjacent to some veins; advanced argillic alteration (kaolinite-alunite) may form<br />
along the tops <strong>of</strong> mineralized zones. Propylitic alteration dominates at depth and<br />
peripherally. Panteleyev, A.(1996). Buddingtonite can also be present.<br />
QSA Quartz-Sericite-<br />
Adularia<br />
Figure 21 - Plot shows illite, mixed layer<br />
illite/smectite, montmorillonite, quartz, calcite,<br />
dolomite, kaolinite and pyrite.<br />
20<br />
Silicic<br />
Figure 22 - Silicic alteration is pervasive<br />
replacement <strong>of</strong> the rock by silica minerals.<br />
Minerals include opal, chalcedony, quartz,<br />
hematite, and pyrite.
________________________________________________________________<br />
This assemblage also contains adularia. The chemical bonds for feldspars are<br />
not detectable in the SWIR range. This varies from alteration around veins,<br />
fractures and permeable zones to selective replacement <strong>of</strong> plagioclase in<br />
alteration envelopes.<br />
Figure 23 - QSA alteration plot shows quartz, illite,<br />
muscovite with quartz, and pyrite.<br />
Argillic<br />
QSA Quartz-Sericite-Adularia<br />
This type <strong>of</strong> alteration occurs as wall rock alteration around veins and<br />
replacement zones in permeable lithologies. This may show the change in<br />
aluminum content and temperature change away from the vein in a progression<br />
from illite illite/smectite smectite. Carbonates are also important in these<br />
systems and may reflect condensation <strong>of</strong> CO2 from deeper boiling zones.<br />
In these systems is also seen amethyst, quartz pseudomorphs after calcite,<br />
barite, fluorite, Ca-Mg-Mn-Fe carbonate minerals such as rhodochrosite.<br />
Panteleyev (1996):<br />
21<br />
Argillic<br />
Figure 24 - Argillic alteration plot shows<br />
illite, illite/smectite, montmorillonite,<br />
calcite, dolomite, kaolinite, and pyrite.
________________________________________________________________<br />
Steam Heated Argillic<br />
This alteration type is found above the water table and forms an extensive area.<br />
It is related to the condensation and oxidation <strong>of</strong> gases (H2S). It is found in<br />
geothermal areas with mud pots, fumeroles and native sulfur.<br />
Weathered outcrops are <strong>of</strong>ten characterized by resistant quartz ± alunite 'ledges'<br />
and extensive flanking bleached, clay-altered zones with supergene alunite,<br />
jarosite, and other limonite minerals. Panteleyev (1996):<br />
Propyllitic<br />
Steam Heated Argillic<br />
Figure 25 - Steam Heated Argillic alteration<br />
plots sulfur, pyrite, chalcedony, opal,<br />
kaolinite, alunite and jarosite.<br />
Propylitic alteration occurs in the outer zone <strong>of</strong> alteration around a deposit. It can<br />
have regional extension.<br />
22<br />
Propylitic<br />
Figure 26 - This plot <strong>of</strong> propylitic alteration shows<br />
Mg-Chlorite, Fe-Chlorite, epidote, illite/smectite,<br />
zeolite. Montmorillonite and calcite.
________________________________________________________________<br />
Definition <strong>of</strong> deposit type<br />
HIGH SULFIDATION SYSTEMS<br />
High sulphidation Au + Cu ore systems develop from the reaction with host rocks<br />
<strong>of</strong> hot acidic magmatic fluids to produce characteristic zoned alteration and later<br />
sulphide and Au + Cu + Ag deposition. Ore systems display permeability controls<br />
governed by lithology, structure and breccias and changes in wall rock alteration<br />
and ore mineralogy with depth <strong>of</strong> formation. One <strong>of</strong> the challenges is to<br />
distinguish the mineralized systems from a group <strong>of</strong> generally non-economic<br />
acidic alteration styles including lithocaps or barren shoulders, steam heated,<br />
magmatic solfatara and acid sulphate alteration.<br />
Original definitions (Heald et al.,1987) suggest that epithermal deposits formed at<br />
temperatures < 300°C and therefore at shallow depths, typically < 1 km.<br />
The term epithermal is therefore used in <strong>field</strong> exploration studies to describe Au ±<br />
Ag ± Cu deposits formed in magmatic arc environments (including rifts) at<br />
shallow depths, most typically above the level <strong>of</strong> formation <strong>of</strong> porphyry Cu-Au<br />
deposits (typically < 1 km), although in many instances associated with<br />
subvolcanic intrusions. Higher level epithermal deposits are commonly formed<br />
later in a deposit paragenesis, and may be telescoped upon deeper earlier<br />
formed deposits, including in some instances porphyry systems which are older,<br />
or part <strong>of</strong> the same overall magmatic event (e.g., Lihir, Corbett et al., 2001b). In<br />
strongly dilational structural environments porphyry-related systems may be<br />
telescoped outwards into the deeper “epithermal” environment (e.g., Cadia,<br />
Maricunga Belt).<br />
In brief, high sulphidation deposits develop in settings where volatile rich<br />
magmatic fluids rise to higher crustal levels without significant interaction<br />
with the host rocks or ground waters. Volatiles (SO2) evolved from the<br />
depressurising fluids oxidize to form a two stage hot acid fluid, the initial stage<br />
<strong>of</strong> which reacts with the host rocks to produce the characteristic zoned acidic<br />
alteration at epithermal crustal levels (Corbett and Leach, 1998). A later liquiddominated<br />
fluid phase deposits sulphides which are characterised by pyrite<br />
with enargite, or the latter’s low temperature polymorph luzonite.<br />
Magmatic rocks are interpreted to represent the ultimate source <strong>of</strong> ore fluids as<br />
demonstrated by the commonly association <strong>of</strong> HS deposits with felsic domes<br />
and phreatomagmatic breccias within flow-dome complexes. Many HS deposits<br />
display associations with porphyry Cu-Au systems <strong>of</strong> similar ages (Nena), or are<br />
collapsed upon and form part <strong>of</strong> the porphyry ores. Fluids responsible for the<br />
formation <strong>of</strong> HS deposits rarely evolve to Au- rich lower sulphidation style ores.<br />
23
________________________________________________________________<br />
Model for High Sulfidation Gold Systems<br />
Figure 24 - FUIIIIIIIIIIIIIIIIIIIIIYiuuuuuuuuuuuuuuuuuuuuuuu<br />
Figure 27 - Model for High Sulfidation Gold System showing alteration zones and feeder<br />
structure. Source: Henley and Ellis, 1983<br />
List <strong>of</strong> Well Known Deposits - Distribution<br />
GOLDFIELD , Nevada ZIJINSHAN, China<br />
YANACOCHA, Peru SIPAN, Peru<br />
SUMMITVILLE, Colorado TAMBO, Chile<br />
LEPANTO, Phillipines TANTAHUATAY, Peru<br />
PASCUA-LLAMA, Chile-Argentina AQUA RICA, Argentina<br />
PIERINA, Peru QUIMSACOCHA, Ecuador<br />
PUEBLO VIEJO, Dominican Republic MARTABE, Indonesia<br />
ALTA CHACAMA< Peru VELADERO, Argentina<br />
LA COIPA, Chile RODIQUILAR, Spain<br />
MULATOS, Mexico FURTEI, Sardinia<br />
ALTERATION TYPES (Corbett 2000)<br />
Acid alteration contains a suite <strong>of</strong> minerals formed in low-pH conditions (e.g.,<br />
kaolin-dickite, alunite, pyrophyllite, dickite) and may be grouped as styles<br />
including: Barren high sulphidation alteration described as lithocaps or barren<br />
shoulders are a common source <strong>of</strong> difficulty for explorationists, especially as<br />
these may crop out in the vicinity <strong>of</strong> low and high-sulphidation epithermal Au and<br />
also porphyry Cu-Au mineralization. Barren shoulders comprise a class <strong>of</strong> nonmineralized<br />
advanced argillic (silica-alunite + pyrophyllite etc.) alteration derived<br />
24
________________________________________________________________<br />
from magmatic volatiles venting from intrusive sources at depth (Corbett and<br />
Leach, 1998). These alteration zones are characterized by high temperature<br />
minerals such as pyrophyllite-diaspore, zunyite, topaz, locally including<br />
corundum and andalusite. Silica characteristically occurs as a massive form<br />
rather than vuggy silica, typical <strong>of</strong> mineralized high sulphidation deposits.<br />
Examples include Lookout Rocks, Horse Ivaal at Frieda River, Vuda, and Alum<br />
Mountain. Lithocaps (Sillitoe (1995, 1999) may extend to higher crustal levels,<br />
include additional lower temperature argillic alteration, and are interpreted<br />
(Sillitoe, op cit) to locally conceal epithermal or porphyry mineralization.<br />
Shoulders and lithocaps crop out as variably dipping bodies termed ledges<br />
developed by the exploitation <strong>of</strong> permeable lithologies (typically flat dipping), or<br />
dilatant structures (typically steep dipping). These alteration zones are<br />
distinguished from mineralized high sulphidation systems in the <strong>field</strong> by the lack<br />
<strong>of</strong> vuggy silica and generally coarse grained and higher temperature layered<br />
silicates (e.g., alunite, pyrophyllite, dickite). The presence <strong>of</strong> high temperature<br />
alteration minerals such as alunite or corundum is distinctive. PIMA, Terraspec<br />
and XRD studies are therefore useful for the delineation <strong>of</strong> alteration zonation<br />
and pro<strong>vis</strong>ion <strong>of</strong> vectors towards where mineralization should occur in ore<br />
systems.<br />
25
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Alteration Types Associated with High Sulfidation Systems<br />
Vuggy Silica<br />
This alteration type occurs in structural zones or as replacement bodies in<br />
permeable lithologies, usually in the core <strong>of</strong> zones <strong>of</strong> advanced argillic alteration.<br />
This extreme form <strong>of</strong> acid leaching occurs in the higher levels <strong>of</strong> epithermal<br />
deposits. It is also found in the upper parts <strong>of</strong> telescoped porphyry systems.<br />
Figure 28 - Vuggy Silica Alteration shows alunite,<br />
jarosite, quartz, sulfur, pyrite, hematite.<br />
Silicic<br />
Vuggy Silica<br />
Silicification adds silica to a vuggy, acid leached rock and fills the vugs created<br />
through intense leaching. Silicification is common in high sulfidation systems. It<br />
can be confused with intense quartz stockwork at the top <strong>of</strong> some porphyry<br />
deposits.<br />
. Advanced Argillic<br />
This alteration type is found in the upper regions <strong>of</strong> a high sulfidation system. It<br />
can occur in the lithocap <strong>of</strong> a porphyry system.<br />
The progressive neutralization and cooling <strong>of</strong> high sulphidation fluids by rock<br />
reaction produces alteration moving away from the core in which zonation is<br />
characterized progressively outwards by mineral assemblages dominated by:<br />
alunite, pyrophyllite, kaolin, and illitic and chloritic clays (Corbett and Leach,<br />
26<br />
Silicic<br />
Figure 29 - The silicic alteration plot shows quartz,<br />
chalcedony, alunite, barite, hematite, pyrite.<br />
Barite has only water features and does not have<br />
a diagnostic spectrum.
________________________________________________________________<br />
1998). Mineralogies dominated by pyrophyllite-diaspore-dickite may be<br />
indicative, but not exclusively, <strong>of</strong> higher temperature (deeper) conditions,<br />
whereas lower temperature (opaline) pervasive silicification or alunite-kaolin<br />
dominate in cooler (higher level) settings. Similarly, thin alteration zones may<br />
suggest that fluid conditions have changed rapidly, possibly in a quenched higher<br />
level system (or distal to the fluid upflow), whereas wide zonation characterizes<br />
slower changing fluid conditions more typical <strong>of</strong> deeper levels (or more proximal<br />
to the fluid upflow).<br />
Figure 30 - Advanced Argillic Alteration spectra show<br />
pyrophyllite, topaz, zunyite, dickite, alunite, quartz,<br />
hematite, and pyrite.<br />
27<br />
Figure 31 - Intermediate Argillic Alteration shows<br />
kaolinite, illite, illite/smectite, montmorillonite, quartz,<br />
pyrite
________________________________________________________________<br />
Argilic — Intermediate Argillic<br />
This alteration zone is found between propylitic and and advanced argillic. It can<br />
be progressive outward from illite illite/smectite montmorillonite. It may<br />
also show gradations from illite + illite/smectite into a chlorite envelope<br />
around the illite vein (Comstock Lode, Virginia City, Nv).<br />
Figure 32 - Argillic alteration contains<br />
kaolinite, illite, illite/smectite,<br />
montmorillonite, quartz, and pyrite.<br />
Propylitic Alteration<br />
Propylitic can be regional, but it is usually found in the outer-most alteration<br />
zone. It will show different wavelengths for the chlorites as opposed to those<br />
chlorites in the intermediate argillic suite.<br />
28<br />
Figure 33 - Propylitic Alteration shows Mg-Chlorite,<br />
Fe-chlorite, epidote, calcite, pyrite.
________________________________________________________________<br />
Porphyry Copper Deposits<br />
Porphyry copper deposits form at 2-5 km below the earth's surface at<br />
temperatures <strong>of</strong> >500-600 degreed C from hypersaline (40-60 wt % NaCl equiv.)<br />
near neutral magmatic fluids (Hedenquist and Lowenstein, 1994). Aqueous<br />
magmatic vapors containing CO2, SO2, H2S, and HCl separate from fluids and<br />
ascend to the surface. Ore bodies range in size from several hundred meters to<br />
more than a kilometer in diameter. Grades tend to be low, and the ore minerals<br />
are usually disseminated through a quartz stockwork within the upper part <strong>of</strong> the<br />
host porphyry intrusive.<br />
Alteration around the ore body is usually concentric and may be described by the<br />
Lowell and Guilbert (1970) model for porphyry copper deposits. Zoned<br />
assemblages that were formed as reactive, metal-bearing magmatic fluid, which<br />
moved away from the intrusion, cooled and reacted with the country rock.<br />
In the core <strong>of</strong> the deposit, over the mineralizing intrusion, there is a potassic zone<br />
(biotite + magnetite ± orthoclase ± albite ± anhydrite ± chalcopyrite ± bornite)<br />
which represents late magmatic K-metasomatism <strong>of</strong> the host intrusives. This<br />
passes upwards into extensive quartz stockwork and a transitional zone<br />
characterized by intermediate argillic alteration (chlorite + hematite/sulfides +<br />
quartz ± illite).<br />
This is usually overprinted by the phyllic zone which dominates the stockwork.<br />
The phyllic zone is acid-leached and characterized by quartz + sericite +<br />
tourmaline + pyrite ± chalcopyrite. The sericite may be composed <strong>of</strong> either illite +<br />
montmorillonite or fine grained muscovite. Above the phyllic zone, the rock is<br />
capped by an advanced argillic zone where leaching is oxidized acidic water<br />
(generated by the absorption <strong>of</strong> magmatic vapor in to meteoric waters) has been<br />
particularly intense and may reach to the paleosurface. It is characterized by the<br />
assemblage quartz + alunite ± pyrophyllite ± kaolinite/dickite. Surrounding the<br />
potassic, intermediate/phyllic and advanced argillic zones is the deuterically<br />
(propylitic) altered country rock. The propylitic zone is characterized by green<br />
coloration and the assemblage: chlorite + epidote ± albite ± actinolite ± calcite ±<br />
hematite.<br />
Hypogene copper sulphide mineralization is characterized by chalcopyrite<br />
[although bornite occurs when the sulfur activity is low as indicated by the<br />
absence <strong>of</strong> pyrite]. Magnetite is common in the potassic zone and pyrite in<br />
phyllic zone in the advanced argillic zone, sulphides have been decomposed and<br />
leached, or replaced by limonite.<br />
Supergene leaching <strong>of</strong> hypogene alteration and mineralization occurs after the<br />
hydrothermal event. It is distinguished here from weak secondary alteration (due<br />
to later near neutral meteoric water percolation) which does not produce strong<br />
leaching, but may result in a modest overprint <strong>of</strong> montmorillonite, kaolinite, in the<br />
29
________________________________________________________________<br />
hypogene and supergene zones. The principal mechanism <strong>of</strong> strong supergene<br />
leaching is the oxidation <strong>of</strong> pyrite in water, which produces limonite and<br />
generates sulphuric acid. The effect <strong>of</strong> this acid on acid stable hypogene<br />
minerals (quartz, alunite, kaolinite) is subtle. However, there may be<br />
decomposition <strong>of</strong> biotite and feldspars in the potassic zone. Feldspars and<br />
chlorite in the propylitic zone and illite in the phyllic zone, producing a supergene<br />
leached cap that is characterized by the assemblage quartz + alunite + kaolinite<br />
+ gypsum. This is not always easy to distinguish from the hypogene leached cap<br />
<strong>of</strong> the advanced argillic zone.<br />
Figure 34<br />
Infrared Active Alteration Minerals Associated with Porphyries<br />
Infrared-active alteration minerals associated with porphyries include quartz,<br />
sericite/muscovite, biotite, phlogopite, anhydrite/gypsum, magnetite, actinolite,<br />
chlorite, epidote, calcite, clay minerals (illite, kaolinite, smectite), tourmaline.<br />
Gangue minerals in mineralized veins are mainly quartz with lesser biotite,<br />
sericite, magnetite, chlorite, calcite, epidote, anhydrite and tourmaline. Leached<br />
cap and lithocap minerals can include jarosite, alunite, pyrophyllite, diaspore,<br />
zunyite, topaz and dickite.<br />
30
________________________________________________________________<br />
Alteration types associated with Porphyry Copper Deposits<br />
ALTERATION MINERALOGY:<br />
Early formed alteration can be overprinted by younger assemblages. Central and<br />
early formed potassic zones (K-feldspar and biotite) commonly coincide with ore.<br />
This alteration can be flanked in volcanic host rocks by biotite-rich rocks that<br />
grade outward into propylitic rocks. The biotite is a fine-grained, “shreddy”<br />
looking secondary mineral that is commonly referred to as an early developed<br />
biotite (EDB) or a “biotite hornfels”. These older alteration assemblages in<br />
cupriferous zones can be partially to completely overprinted by later biotite and<br />
K-feldspar and then phyllic (quartz-sericite-pyrite) alteration, less commonly<br />
argillic, and rarely, in the uppermost parts <strong>of</strong> some ore deposits, advanced argillic<br />
alteration (kaolinite-pyrophyllite) . Panteleyev (1995):<br />
Potassic - biotite rich Alteration (Thompson and Thompson, 1996)<br />
This alteration type is found in the core <strong>of</strong> porphyry deposits. It may form large<br />
peripheral alteration zone in wall rocks (without K-spar) and zones out to<br />
propylitic alteration. Minerals include biotite, phlogopite, K-spar, magnetite,<br />
quartz, anhydrite, albite-sodic plagioclase, actinolite, rutile, apatite, sericite,<br />
chlorite, and epidote.<br />
Figure 35 - Potassic alteration shows<br />
Actinolite, biotite, phlogopite, epidote, ironchlorite,<br />
Mg-chlorite, muscovite, quartz,<br />
anhydrite, magnetite.<br />
31<br />
Figure 36 - Potassic - K-silicate alteration<br />
includes "albite", anhydrite, quartz, muscovite<br />
and epidote.
________________________________________________________________<br />
Potassic - K-silicate<br />
This alteration occurs in the core <strong>of</strong> porphyry systems, particularly when hosted<br />
by felsic intrusions - granodiorite, quartz monzonite,granite, seyenite. Minerals<br />
include K-feldspar, quartz, albite, muscovite, anhydrite, epidote. Feldspars do<br />
not have detectable bonds in the SWIR region and therefore their pr<strong>of</strong>iles do not<br />
have distinctive features.<br />
Sodic, Sodic-Calcic<br />
Occurs with minor mineralization in the deeper parts <strong>of</strong> some porphyry systems<br />
and is a host to mineralization in porphyry deposits associated with alkaline<br />
intrusions.<br />
albite, actinolite, diopside, quartz, magnetite, titanite, chlorite, epidote , scapolite<br />
Figure 37 - Sodic- Calcic alteration plots<br />
Albite, actinolite, Fe-chlorite, epidote,<br />
Mg-chlorite, marialite, mizzonite,<br />
diopside, quartz, magnetite.<br />
32<br />
Figure 38 - Phyllic alteration includes:<br />
Illite, muscovite, iron chlorite, Mgchlorite,<br />
gypsum, anhydrite, quartz,<br />
pyrite.
________________________________________________________________<br />
Phyllic<br />
Phyllic alteration commonly forms a peripheral halo around the core <strong>of</strong> porphyry<br />
deposits. It may overprint earlier potassic alteration and may host substantial<br />
mineralization. Detectable minerals include muscovite, illite, quartz, pyrite,<br />
chlorite, hematite, and anhydrite.<br />
Intermediate Argillic<br />
Intermediate argillic alteration generally forms a structurally controlled to<br />
widespread overprint on other types <strong>of</strong> alteration in many porphyry systems. The<br />
detectable minerals include illite, muscovite, dickite, kaolinite, Fe-chlorite, Mgchlorite,<br />
epidote, montmorillonite, calcite, and pyrite.<br />
Figure 39 - Intermediate argillic alterations<br />
contains muscovite, illite, chlorite, kaolinite,<br />
dickite, montmorillonite, calcite, epidote, and<br />
pyrite.<br />
33<br />
Figure 40 - Advanced argillic alteration for a<br />
porphyry system will contain higher temperature<br />
minerals such as Topaz, pyrophyllite, andalusite,<br />
dumortierite, tourmaline, along with alunite,<br />
diaspore, quartz, hematite, and pyrite.
________________________________________________________________<br />
Advanced Argillic<br />
This is an intense alteration phase, <strong>of</strong>ten in the upper part <strong>of</strong> porphyry systems.<br />
It can also form envelopes around pyrite-rich veins that cross cut other alteration<br />
types. The minerals associated with this type are higher temperature and include<br />
pyrophyllite, quartz, andalusite, diaspore, corundum, alunite, topaz, tourmaline,<br />
dumortierite, pyrite, and hematite.<br />
Propylitic<br />
Forms the outermost alteration zone at intermedite to deep levels in the porphyry<br />
system. It can be mineralogically zoned from inner actinolite-rich to out epidote<br />
rich facies. chlorite, epidote, albite, calcite, actinolite, illite, clay pyrite<br />
Figure 41 - Propylitic alteration for porphyry systems<br />
includes; Fe- chlorite, Mg-chlorite, epidote, actinolite,<br />
calcite, illite, montmorillonite, albite, and pyrite.<br />
34<br />
Figure 42 - Copper carbonates in porphyry<br />
systems can include azurite, malachite,<br />
aurichalcite, and rosasite.
ARSENATES<br />
________________________________________________________________<br />
Supergene<br />
Secondary (supergene) zones carry chalcocite, covellite and other Cu2S minerals<br />
(digenite, djurleite, etc.), chrysocolla, native copper and copper oxide, carbonate<br />
and sulphate minerals. Oxidized and leached zones at surface are marked by<br />
ferruginous “cappings” with supergene clay minerals, limonite (goethite, hematite<br />
and jarosite) and residual quartz. Panteleyev, A. (1995):<br />
Minerals include: antlerite, bisbeeite, brochantite, chalcoalumite, claringbullite,<br />
conichalcite, crednerite, cuprite, delafossite, graemite, nantokite, paramelaconite,<br />
paratacamite, rosasite and spangolite, aurichalcite, connellite, cyanotrichite,<br />
malachite and shattuckite are additional supergene copper. Those available in<br />
the database are plotted in this section.<br />
The best way to display the variations in the supergene environment is by group.<br />
The following plots are divided into copper carbonates, chlorides, arsenates,<br />
phosphate, silicates and sulfates.<br />
CHLORIDES<br />
Figure 43 - Copper chlorides includes<br />
atacamite, connellite, and cumengite.<br />
ARSENATES<br />
35<br />
PHOSPHATES<br />
Figure 44 - Copper phosphates include<br />
libelhenite, pseudomalachite, and<br />
turquoise.<br />
Figure 45 - Copper arsenates<br />
include bayldonite, chenevixite,<br />
conichalcite, clinoclase and<br />
olivenite.
________________________________________________________________<br />
SILICATES<br />
Figure 46 - Copper silicates include chrysocolla,<br />
dioptase, papagoite, and shattuckite<br />
36<br />
SULFATES<br />
Figure 47 - Copper sulfates include antlerite,<br />
brochantite, chalcanthite, cyanotrichite,<br />
kroehnite, spangolite.
________________________________________________________________<br />
LEACHED CAP<br />
Minerals in the leached cap environment include alunite, kaolinite, illite, diaspore,<br />
iron oxides, copper sulfates, and copper hydroxides.<br />
Figure 48 - Leach cap minerals include goethite,<br />
hematite, jarosite, kaolinite, chrysocolla,<br />
antlerite, brochantite, diaspore, turquoise.<br />
alunite.<br />
Exotic copper mineralization is a complex hydrochemical process linking<br />
supergene enrichment, lateral copper transport, and precipitation <strong>of</strong> copper oxide<br />
minerals in the drainage network <strong>of</strong> a porphyry copper deposit.<br />
37<br />
Figure 49 - Other leach cap minerals are copper<br />
bearing and include atacamite, azurite, malachite,<br />
chrysocolla, kaolinite.
________________________________________________________________<br />
DIAMONDS - KIMBERLITES<br />
DEPOSIT DEFINITION<br />
Kimberlites are a group <strong>of</strong> volatile-rich (dominantly carbon dioxide) potassic<br />
ultrabasic rocks. Commonly, they exhibit a distinctive inequigranular texture<br />
resulting from the presence <strong>of</strong> macrocrysts (and in some instances megacrysts)<br />
set in a fine-grained matrix. The megacryst/macrocryst assemblage consists <strong>of</strong><br />
rounded anhedral crystals <strong>of</strong> magnesian ilmenite, Cr-poor titanian pyrope, olivine,<br />
Cr-poor clinopyroxene, phlogopite, enstatite and Ti-poor chromite. Olivine is the<br />
dominant member <strong>of</strong> the macrocryst assemblage. The matrix minerals may<br />
include second generation euhedral primary olivine and/or phlogopite, together<br />
with perovskite, spinel (titaniferous magnesian aluminous chromite, titanian<br />
chromite, members <strong>of</strong> the magnesian ulvospinel-ulvospinel-magnetite series),<br />
diopside (Al- and Ti- poor), monticellite, apatite, calcite, and primary late-stage<br />
serpentine (commonly Fe rich). Some kimberlites contain late-stage phlogopites.<br />
The replacement <strong>of</strong> early-formed olivine, phlogopite, monticellite, and apatite by<br />
deuteric serpentine and calcite is common. Evolved members <strong>of</strong> the clan may be<br />
devoid <strong>of</strong>, or poor in, macrocrysts, and composed essentially <strong>of</strong> calcite,<br />
serpentine, and magnetite together with minor phlogopite, apatite, and<br />
perovskite. (From Mitchell 1986)<br />
http://www.geology.ubc.ca/research/diamonds/kopylova/intro/morphology.html<br />
Kimberlites can be divided into 3 distinct units based on morphology and<br />
petrology. These units are: 1) Crater Facies Kimberlite ,2) Diatreme Facies<br />
Kimberlite; 3) Hypabyssal Facies Kimberlite (Mitchell 1986). Kimberlite occurs<br />
in the Earth's crust in vertical structures known as kimberlite pipes.<br />
Kimberlites are divided into Group I (basaltic) and Group II (micaceous)<br />
kimberlites, along mineralogical grounds, the difference in mineralogy being<br />
caused by the preponderance <strong>of</strong> water versus carbon dioxide. Group I<br />
kimberlites are <strong>of</strong> CO2-rich ultramafic potassic igneous rocks dominated by a<br />
primary mineral assemblage <strong>of</strong> forsteritic olivine, magnesian ilmenite, chromian<br />
pyrope, almandine-pyrope, chromian diopside, phlogopite, enstatite and <strong>of</strong> Tipoor<br />
chromite. Group-II kimberlites (or orangeites) are ultrapotassic, peralkaline<br />
rocks rich in volatiles (dominantly H2O). The distinctive characteristic <strong>of</strong><br />
orangeites is phlogopite macrocrysts and microphenocrysts, together with<br />
groundmass micas that vary in composition from phlogopite to Fe-rich<br />
phlogopite.<br />
38
________________________________________________________________<br />
Figure 50<br />
DEPOSIT MODEL<br />
Diamonds are mined in about 25 countries. India was the initial source, followed<br />
by Brazil and then South Africa. Africa is the richest continent for diamond<br />
mining, accounting for roughly 49% <strong>of</strong> world production. The major sources are in<br />
the south with lesser concentrations in the west-central part <strong>of</strong> the continent. The<br />
major producing countries are Congo Republic (Zaire), Botswana, South Africa,<br />
<strong>An</strong>gola, Namibia, Ghana, Central African Republic, Guinea, Mali, Sierra Leone,<br />
Tanzania and Zimbabwe. Canada is starting to come on line now with Ekati and<br />
Diavik.in the northern part <strong>of</strong> the country. Australia has one producing mine, the<br />
Argyle. There are major resources in Russia. The United States has very minor<br />
deposits in Colorado, Wyoming and Arkansas.<br />
(http://www.amnh.org/exhibitions/diamonds/other.html)<br />
39
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ALTERATION MINERALS<br />
Common alteration minerals associated with kimberlites include: Carbonates,<br />
Phlogopite, Biotite, chlorites, Serpentine, richterite, other amphiboles, talc,<br />
septechlorite, smectite, saponite, apophyllite, zeolites (analcime), vermiculite.<br />
Figure 51 - This plots shows Serpentine,<br />
calcite, magnesite, phlogopite, biotite,<br />
chamosite, clinochlore, saponite, Mgsilicate,<br />
vermiculite, Fe-amphibole.<br />
INDICATOR MINERALS<br />
Several minerals, when found in glacial sediments, are useful indicators <strong>of</strong> the<br />
presence <strong>of</strong> kimberlite, and to a certain extent, an evaluation <strong>of</strong> the diamond<br />
potential <strong>of</strong> kimberlite. These minerals are far more abundant in kimberlite than<br />
diamond, survive glacial transport, and are <strong>vis</strong>ually and chemically distinct. Crpyrope<br />
(purple colour, kelyphite rims), eclogitic garnet (orange-red), Cr-diopside<br />
(pale to emerald green), Mg-ilmenite (black, conchoidal fracture), chromite<br />
40<br />
Figure 52 - Other alteration minerals include<br />
pyrope garnet, richterite, phlogopite, olivine,<br />
diopside. Cr-diopside
________________________________________________________________<br />
(reddish-black, irregular to octahedral crystal shape), and olivine (pale yellowgreen)<br />
are the most commonly used kimberlite indicator minerals in drift<br />
prospecting. Kimberlite indicator minerals are recovered from the medium to very<br />
coarse sand-sized fraction <strong>of</strong> glacial sediments, and analyzed by electron<br />
microprobe to confirm their identification.<br />
(source: http://sts.gsc.nrcan.gc.ca/page1/miner/kirk/indic.htm)<br />
Garnets<br />
Pyrope, Almandine, Grossular<br />
Diopside<br />
Chrome-diopside, diopside<br />
Others to consider<br />
Zircon, Olivine, Orthopyroxenes (Harzburgite?),Chromite??, Ilmenite??,<br />
Perovskite??<br />
Figure 53 - This plot includes<br />
almandine, grossularite, pyrope garnets;<br />
diopside, Cr-diopside, and olivine. Figure 54 - Garnet comparisons<br />
\<br />
41<br />
The indicator garnet for the presence <strong>of</strong> diamonds in<br />
kimberlites is a G-10. This has a diagnostic chrome<br />
feature in the <strong>vis</strong>ible, indicated by the arrow.
________________________________________________________________<br />
DEPOSIT TYPE DEFINITION<br />
SKARNS<br />
http://www.wsu.edu:8080/~meinert/aboutskarn.html#Definitions<br />
There are many definitions and usages <strong>of</strong> the word "skarn". Skarns can form<br />
during regional or contact metamorphism and from a variety <strong>of</strong> metasomatic<br />
processes involving fluids <strong>of</strong> magmatic, metamorphic, meteoric, and/or marine<br />
origin. They are found adjacent to plutons, along faults and major shear zones, in<br />
shallow geothermal systems, on the bottom <strong>of</strong> the seafloor, and at lower crustal<br />
depths in deeply buried metamorphic terranes. What links these diverse<br />
environments, and what defines a rock as skarn, is the mineralogy. This<br />
mineralogy includes a wide variety <strong>of</strong> calc-silicate and associated minerals but<br />
usually is dominated by garnet and pyroxene.<br />
The composition and texture <strong>of</strong> the protolith tend to control the composition and<br />
texture <strong>of</strong> the resulting skarn. In contrast, most economically important skarn<br />
deposits result from large-scale metasomatic transfer, where fluid composition<br />
controls the resulting skarn and ore mineralogy.<br />
One <strong>of</strong> the more fundamental controls on skarn size, geometry, and style <strong>of</strong><br />
alteration is the depth <strong>of</strong> formation.<br />
Major skarn types:<br />
Fe Skarns ,Au Skarns, W Skarns, Cu Skarns, Zn Skarns, Mo Skarns.<br />
The vast majority <strong>of</strong> skarn deposits are associated with magmatic arcs related to<br />
subduction beneath continental crust. Plutons range in composition from diorite<br />
to granite although differences among the main base metal skarn types appear to<br />
reflect the local geologic environment (depth <strong>of</strong> formation, structural and fluid<br />
pathways) more than fundamental differences <strong>of</strong> petrogenesis (Nakano et al.,<br />
1994). In contrast, gold skarns in this environment are associated with<br />
particularly reduced plutons that may represent a restricted petrologic history.<br />
42
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ALTERATION TYPES ASSOCIATED WITH SKARNS<br />
RETROGRADE ALTERATON<br />
The term retrograde alteration refers to an alteration stage in which higher<br />
temperature, generally anhydrous, minerals are replaced by lower temperature,<br />
generally hydrous, minerals. In some cases this process is largely metamorphic,<br />
i.e. the bulk composition stays roughly the same but mineral "A" is replaced by<br />
mineral "B". In other cases, retrograde alteration is concurrent with strong<br />
metasomatism, such as during mineralization with various sulfide minerals<br />
Retrograde skarn mineralogy, in the form <strong>of</strong> epidote, amphibole, chlorite, and<br />
other hydrous phases, typically is structurally controlled and overprints the<br />
prograde zonation sequence. Thus, there <strong>of</strong>ten is a zone <strong>of</strong> abundant hydrous<br />
minerals along fault, stratigraphic, or intrusive contacts. This superposition <strong>of</strong><br />
later phases can be difficult to discriminate from a spatial zonation sequence due<br />
to progressive reaction <strong>of</strong> a metasomatic fluid.<br />
SKARN MODEL<br />
Figure 55 - Zonation <strong>of</strong> most skarns reflects the geometry <strong>of</strong> the pluton<br />
contact and fluid flow. Such skarns are zoned from proximal endoskarn to<br />
proximal exoskarn, dominated by garnet. More distal skarn usually is more<br />
pyroxene-rich and the skarn front, especially in contact with marble, may be<br />
dominated by pyroxenoids or vesuvianite. Meinert, L.D., 1992<br />
43
________________________________________________________________<br />
In general, retrograde alteration is more intense and more pervasive in shallower<br />
skarn systems. In some shallow, porphyry copper-related skarn systems,<br />
extensive retrograde alteration almost completely obliterates the prograde garnet<br />
and pyroxene skarn (Einaudi, 1982a,b)<br />
Porphyry copper Skarn<br />
Alteration potassic alteration<br />
phillic alteration<br />
advanced argillic alteration<br />
propylitic alteration<br />
Figure 56 - From Murakami (2005)<br />
The main differences between amphiboles in different skarn types are variations<br />
in the amount <strong>of</strong> Fe, Mg, Mn, Ca, Al, Na, and K. Amphiboles from Au, W, and Sn<br />
skarns are progressively more aluminous (actinolite-hastingsite-hornblende),<br />
amphiboles from Cu, Mo, and Fe skarns are progressively more iron-rich in the<br />
tremolite-actinolite series, and amphiboles from zinc skarns are both Mn-rich and<br />
Ca-deficient, ranging from actinolite to dannemorite. For a specific skarn deposit<br />
or group <strong>of</strong> skarns, compositional variations in less common mineral phases,<br />
such as idocrase, bustamite, or olivine, may provide insight into zonation patterns<br />
or regional petrogenesis (e.g. Giere, 1986; Silva and Siriwardena, 1988;<br />
Benkerrou and Fonteilles, 1989).<br />
44<br />
Prograde<br />
Retrograde<br />
Vein system A vein:biotite vein<br />
Dominant in sallower part <strong>of</strong><br />
B vein:Quartz-molybdenite (no alteration halo skarn system<br />
along vein)<br />
C vein:chlorite (or green smectite bearing<br />
mixed layer clay) + sulfides (partly pyrite<br />
+molybdenite)<br />
D vein: phillic alteration (sericite alteration<br />
along Quartz vein)<br />
Related intrusion Generally, porphyry, sometimes depend on<br />
depth <strong>of</strong> formation<br />
Depend on depth <strong>of</strong> formation
________________________________________________________________<br />
PROGRADE ALTERATION<br />
The minerals found in prograde systems include: Scapolite-meionite, scapolitemarialite,<br />
scapolite-mizzonite, diopside, hedenbergite, olivine, rhodonite,<br />
grossularite, andradite, wollastonite, vesuvianite<br />
Figure 57 - Scapolite-meionite, scapolite-marialite, scapolite-mizzonite, diopside, hedenbergite,<br />
olivine, rhodonite, grossularite, andradite, wollastonite, and vesuvianite.<br />
45
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RETROGRADE SKARN ALTERATION<br />
Retrograde alteration commonly replaces earlier skarn alteration, but may also<br />
affect adjacent wallrock, which is many cases is limestone.<br />
The minerals observed in these suites include illite/smectite, montmorillonite,<br />
nontronite, pyrite, epidote, clinozoisite, tremolite ->actinolite, prehnite, chlorite,<br />
vesuvianite, biotite, phlogopite, quartz, calcite, dolomite, ankerite, siderite, Fedolomite.<br />
These are plotted in Figures 58, 59, and 60.<br />
CLAY SERIES<br />
Figure 58 - Illite, Illite/smectite,<br />
montmorillonite, nontronite, and pyrite.<br />
46<br />
CARBONATE SERIES<br />
Figure 59 - <strong>An</strong>kerite, calcite, dolomite,<br />
Fe-dolomite, and siderite.
________________________________________________________________<br />
Figure 60 - Actinolite, tremolite, epidote,<br />
clinozoisite, Fe-Chlorite, Mg-chlorite,<br />
biotite, phlogopite, vesuvianite, and<br />
prehnite<br />
47<br />
Figure 61 - Forsterite, serpentine, talc, calcite,<br />
tremolite, and magnetite<br />
MAGNESIUM SKARN<br />
Magnesium skarns are developed as<br />
metasomatic replacements <strong>of</strong> dolomitic<br />
limestone. High temperature magnesium<br />
skarns are characterized by forsterite, and<br />
diopside and low temperature magnesium<br />
skarns contain serpentine and talc. Both <strong>of</strong><br />
which occur as retrograde minerals after<br />
forsterite and clinopyroxene.<br />
Figure 61 plots forsterite, serpentine, talc,<br />
calcite, tremolite, magnetite.
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Definition <strong>of</strong> deposit type<br />
IRON OXIDE COPPER GOLD (IOCG)<br />
Iron oxide copper-gold (IOCG) deposits encompass a wide spectrum <strong>of</strong> sulphidedeficient<br />
low-Ti magnetite and/or hematite ore bodies <strong>of</strong> hydrothermal origin<br />
where breccias, veins, disseminations and massive lenses with polymetallic<br />
enrichments (Cu, Au, Ag, U, REE, Bi, Co, Nb, P) are genetically associated with,<br />
but either proximal or distal to large-scale continental, A- to I-type magmatism,<br />
alkaline-carbonatite stocks, and crustal-scale fault zones and splays. The<br />
deposits are characterized by more than 20% iron oxides. Their lithological hosts<br />
and ages are non-diagnostic but their alteration zones are, with calcic-sodic<br />
regional alteration superimposed by focused potassic and iron oxide alterations.<br />
The deposits form at shallow to mid crustal levels in extensional, anorogenic or<br />
orogenic, continental settings such as intracratonic and intra-arc rifts, continental<br />
magmatic arcs and back-arc basins. Margins <strong>of</strong> Archean craton where arcs and<br />
successor arcs were developed appear to be particularly fertile.<br />
http://gsc.nrcan.gc.ca/mindep/synth_dep/iocg/index_e.php<br />
The 3810 Mt Olympic Dam deposit in Australia is the deposit that guides most<br />
mineral exploration worldwide (Hitzman et al., 1992; Western Mining Corporation,<br />
2003). Currently known metallogenic IOCG districts occur in Precambrian<br />
shields worldwide as well as in Circum-Pacific regions (e.g., Carlon, 2000;<br />
Fourie, 2000; Porter, 2000, 2002a and papers therein; Strickland and Martyn,<br />
2002; Gandhi, 2004c; G<strong>of</strong>f et al., 2004).<br />
The recognition <strong>of</strong> this deposit type was triggered by the 1975 discovery <strong>of</strong> the<br />
giant Olympic Dam deposit in Australia (Roberts and Hudson, 1983) followed by<br />
the discovery <strong>of</strong> Starra (1980), La Candelaria (1987), Osborne (1988), Ernest-<br />
Henry (1991), and Alemao (1996). The early discoveries served to define this<br />
group <strong>of</strong> deposits as the IOCG deposit type in the 1990s (Hitzman et al., 1992).<br />
source: Mineral Deposits <strong>of</strong> Canada<br />
Source: Iron Oxide Copper-Gold (+/-Ag,+/-Nb,+/-REE,+/-U) Deposits: A Canadian<br />
Perspective<br />
Louise Corriveau Geological Survey <strong>of</strong> Canada<br />
http://gsc.nrcan.gc.ca/mindep/synth_dep/iocg/index_e.php<br />
This appears to be a website publication only.<br />
48
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IOCG PROPOSED MODELS<br />
Figure 62 - Schematic illustrations <strong>of</strong> flow paths and hydrothermal features for alternative models for IOCG deposits. Shading in arrows<br />
indicates predicted quartz precipitation (veining) for different paths in different quartz-saturated rocks which provides a useful<br />
first-order indication <strong>of</strong> path (cf,. Barton el al., 1997, Barton and Johnson,2000)..<br />
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Page 49
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ALTERATION<br />
Following is a summary <strong>of</strong> alteration zoning associated with many IOCG<br />
deposits. Please note that reflectance <strong>spectroscopy</strong> does not detect the silicate<br />
bonds found in the feldspars.<br />
The principal ore minerals are hematite (specularite, botryoidal hematite and<br />
martite), low-Ti magnetite, bornite, chalcopyrite, chalcocite and pyrite.<br />
Subordinate ones include Ag-, Cu-, Ni-, Co-, U-arsenides, autunite, bastnaesite,<br />
bismuthinite, brannerite, britholite, carrolite, cobaltite, c<strong>of</strong>finite, covellite, digenite,<br />
florencite, loellingite, malachite, molybdenite, monazite, pitchblende, pyrrhotite,<br />
sulphosalts, uraninite, xenotime, native bismuth, copper, silver and gold, Ag-, Bi-,<br />
Co-telluride, and vermiculite.<br />
Gangue mineralogy consists principally <strong>of</strong> albite, K-feldspar, sericite, carbonate,<br />
chlorite, quartz (crypto-crystalline in some cases), amphibole, pyroxene, biotite<br />
and apatite (F- or REE-rich) with accessory allanite, barite, epidote, fayallite,<br />
fluorite, ilvaite, garnet, monazite, perovskite, phlogopite, rutile, scapolite, titanite,<br />
and tourmaline. The amphibole includes Fe-, Cl-, Na- or Al-rich hornblende<br />
(edenite), actinolite, grunerite, hastingsite, and tschermakitic or alkali amphibole.<br />
Carbonates include calcite, ankerite, siderite and dolomite. Late-stage veins<br />
contain fluorite, barite, siderite, hematite and sulphides.<br />
There are 3-6 alteration types associated with IOCG deposits. These include<br />
sodic, sodic-calcic, potassic, quartz-tourmaline, and albite-calcite. Figure 63<br />
shows the minerals associated with the different alteration types.<br />
MINERAL Sodic Sodic-calcic Potassic Qzt-Tourmaline Albite-Calcite<br />
albite<br />
K-spar<br />
amphiboles<br />
bastnaesite (REE carbonates)<br />
biotite<br />
calcite<br />
chlorite<br />
epidote<br />
garnet (andradite, Fe-rich garnet)<br />
hematite<br />
monazite<br />
muscovite<br />
quartz<br />
scapolite<br />
tourmaline<br />
magnetite<br />
Figure 63 – Minerals associated with alteration types for IOCG deposits.<br />
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Page 50
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Sodic Alteration. The minerals are albite, magnetite, and epidote.<br />
Sodic<br />
Alteration<br />
Figure 64 - With sodic alteration,<br />
<strong>spectroscopy</strong> sees magnetite and epidote.<br />
Sodic-Calcic Alteration early stages<br />
There is strong albitization (± clinopyroxene, titanite, calc-silicate (clinopyroxene,<br />
amphibole, garnet) - alkali feldspar (K-feldspar, albite) ± Fe-Cu sulphides, and<br />
various assemblages including albite, actinolite, magnetite, apatite and late<br />
epidote. Ca-rich host-rocks are present, with Fe-rich garnet-clinopyroxene ±<br />
scapolite skarn.<br />
Scapolite-actinolite-magnetite<br />
Albite - actinolite-magnetite<br />
Albite-chlorite-epidote-calcite<br />
This is very complex system or systems.<br />
Iron Stage<br />
This stage is largely sterile except for iron ore and apatite. There is an influx <strong>of</strong><br />
magnetite ± biotite.<br />
51<br />
Sodic-Calcic<br />
Figure 65 – Sodic-calcic alteration is more complex.<br />
The plot shows actinolite, iron-chlorite, epidote,<br />
diopside, magnetite, mizzonite, marialite, calcite<br />
and pyrope.
________________________________________________________________<br />
The minerals include<br />
iron oxide (magnetite and hematite), iron carbonate (siderite and<br />
ankerite) and iron silicate (chlorite and amphibole, in particular grunerite<br />
and hastingsite).<br />
IRON STAGE<br />
Figure 66 - The iron stage <strong>of</strong> alteration shows<br />
biotite, iron-chlorite, cummingtonite, ankerite,<br />
siderite, hematite, and magnetite.<br />
Potassic Alteration<br />
The main ore stage is associated with potassium-iron alteration zones in which<br />
either sericite (at Olympic Dam and Prominent Hill) or K-feldspar (most common)<br />
prevail as the potassic-bearing phase.<br />
K-feldspar-biotite-pyrite-chalcopyrite<br />
At Olympic Dam,<br />
Potassic alteration occurs with hematite, sericite, chlorite, carbonate ± Fe-Cu<br />
sulphides ± uraninite, pitchblende and REE (bastnaesite) minerals prevail. It is<br />
locally superimposed on a magnetite-biotite alteration (Reynolds, 2000; Skirrow<br />
et al., 2002). The intense chloritization destroys the biotite. Quartz, fluorite,<br />
barite, carbonate, orthoclase, epidote and tourmaline can also be present.<br />
Titanite, monazite, perovskite and rutile may occur. The main uranium mineral is<br />
uraninite (pitchblende) with lesser c<strong>of</strong>finite and brannerite.<br />
52<br />
POTASSIC ALTERATION<br />
Figure 67 - Potassic is the most<br />
complex <strong>of</strong> the alteration phases. It<br />
includes tourmaline, biotite, iron-chlorite,<br />
epidote, REE-carbonate, monazite,<br />
muscovite, calcite, hematite, quartz.
________________________________________________________________<br />
Quartz-Tourmaline Alteration<br />
The minerals in this suite include tourmaline-magnetite-quartzchalcopyrite-pyrite,<br />
chlorite, and chalcopyrite.<br />
Quartz-Tourmaline<br />
Alteration<br />
Figure 68 - Quartz-tourmaline alteration<br />
plot with magnetite, quartz, tourmaline,<br />
and Fe-chlorite.<br />
Albite-Calcite Alteration<br />
This phase is post ore - retrograde.<br />
The minerals include albite-calcite-bornite-chalcocite and dolomite in<br />
quartz veining.<br />
53<br />
Albite-Calcite<br />
Figure 69 - Albite-calcite alteration is post-ore<br />
and contains calcite, dolomite, and quartz.
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UNCONFORMITY URANIUM DEPOSITS<br />
Unconformity-associated uranium (U) deposits consist <strong>of</strong> pods, veins, and semimassive<br />
replacements <strong>of</strong> uraninite which are overlain by zoned, quartz<br />
dissolution, kaolinite, sudoite, illite, dravite, quartz alteration halos and located<br />
near unconformities between Paleo- to Mesoproterozoic siliciclastic basins and<br />
metamorphic basement.<br />
In major producing basins (e.g. Athabasca, Kombolgie) the 1-2 km, flat-lying,<br />
and apparently un-metamorphosed, mainly fluvial strata include red to pale tan<br />
quartzose conglomerate, arenite and mudstone deposited from ~1730 to > Au, Pt, Cu, REE and Fe.<br />
(Source: by C.W. Jefferson1, D.J. Thomas2, S.S. Gandhi1, P. Ramaekers3, G.<br />
Delaney4, D. Brisbin2, C. Cutts5, P. Portella5, and R.A. Olson6: Mineral<br />
Deposits <strong>of</strong> Canada, Unconformity Associated Uranium Deposits<br />
http://gsc.nrcan.gc.ca/mindep/synth_dep/uranium/index_e.php)<br />
The paleo-weathered basement immediately below the Athabasca Group has a<br />
vertical pr<strong>of</strong>ile ranging from a few centimeters up to 70 meters thick, with much<br />
deeper pockets and slivers developed along fault zones. The following<br />
description is after Macdonald (1980, 1985). The regolith is variably affected by<br />
diagenetic iron reduction resulting in a bleached zone at the top, interpreted as<br />
hematite removal from the upper "red zone" <strong>of</strong> the paleo-weathered basement<br />
section. This bleached zone, always present immediately below the<br />
unconformity, is composed <strong>of</strong> buff-colored clay and quartz. It crosscuts and<br />
therefore post-dates the red zone beneath. Below this, the upper portion <strong>of</strong> the<br />
regolith pr<strong>of</strong>ile exhibits a strong red hematitic alteration that grades into<br />
underlying greenish chloritic alteration. In pr<strong>of</strong>iles developed on the basement<br />
meta-arkose, a white zone <strong>of</strong> white clay replacement <strong>of</strong> feldspars and mafic<br />
minerals separates the red and green zones. A downward progression from this<br />
kaolinite to illite and chlorite is common through the regolith pr<strong>of</strong>ile.<br />
Discussion continues regarding the respective contributions <strong>of</strong> paleo-weathering,<br />
diagenesis and hydrothermal processes to the alteration preserved at the<br />
unconformity. Cuney et al. (2003) stated that the regolith may represent a redox<br />
front controlled by the degree <strong>of</strong> percolation <strong>of</strong> the oxidized diagenetic brines in<br />
the basement, and that the lack <strong>of</strong> Ce-anomalies is not in favour <strong>of</strong> a lateritic<br />
54
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origin. It is here preferred that the red-green alteration was indeed regional, a<br />
result <strong>of</strong> lateritic weathering as proposed by Macdonald (1980), and was<br />
overprinted by hydrothermal alteration (the white zone <strong>of</strong> Macdonald) that<br />
increases in intensity close to and is genetically related to the bleaching<br />
alteration associated with U deposits (Macdonald, 1985). This interpretation is<br />
based on <strong>field</strong> relationships noted by Macdonald (the white zone transects down<br />
across the red and green along fractures).<br />
Deposit Distribution<br />
The new uranium production is likely to come from deposits in Canada, Australia,<br />
Niger, the United States, and Kazakhstan.<br />
Table III - Global Distribution <strong>of</strong> Uranium Deposits<br />
Olympic Dam Australia breccia<br />
Jabiluka Australia unconformity<br />
Ranger Australia unconformity<br />
Kintyre Australia<br />
Athabasca, Thelon Canada unconformity<br />
Kazakhstan sandstone<br />
Niger, sandstone<br />
Uzbekistan, sandstone<br />
Franceville Basin Gabon sandstone<br />
Karoo Basin). South Africa sandstone<br />
Wyoming, New Mexico USA Sandstone<br />
Alteration mineralogy and geochemistry<br />
Alteration mineralogy and geochemistry <strong>of</strong> Australian and Canadian unconformity<br />
associated deposits and their host rocks in the Athabasca and Thelon basins,<br />
and the Kombolgie Basin have been compared by Miller and LeCheminant<br />
(1985), Kotzer and Kyser (1995), Kyser et al. (2000) and Cuney et al. (2003).<br />
Early work on alteration mineralogy in the Athabasca Basin is exemplified by<br />
Hoeve and Quirt (1984), and Wasilyuk (2002) has set the modern framework <strong>of</strong><br />
exploration clay mineralogy. Intense clay alteration zones surrounding deposits<br />
such as Cigar Lake constitute natural geological barriers to U migration in ground<br />
waters (Percival et al., 1993) and are important geotechnical factors in mining<br />
and ore processing (<strong>An</strong>drade, 2002) Figure 70.<br />
Alteration halos are developed mainly in the siliciclastic strata and range between<br />
two distinctive end member types: 1) quartz dissolution + illite ( NE Athabasca)<br />
55
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(Percival, 1989; <strong>An</strong>drade 2002; Cuney et al., 2003), and 2) silicified (Q2) +<br />
kaolinite + dravite (Key Lake, McArthur River) (Matthews et al. 1997, Harvey and<br />
Bethune, 2000).<br />
Ore-related illitic alteration is reflected in anomalously high illite proportions<br />
(Hoeve et al. 1981a, b, Hoeve and Quirt 1984, Percival et al., 1993) and resultant<br />
anomalous K2O/Al203 ratios in the sandstone (Earle and Sopuck 1989). Sudoite,<br />
an Al-Mg-rich di-tri, octahedral chlorite (Percival and Kodama, 1989), is present<br />
in both alteration types. Local silicification fronts are also present in some <strong>of</strong> the<br />
larger de-silicified alteration systems, e.g. Cigar Lake (<strong>An</strong>drade 2002).<br />
Deposit-related silicification (Q2 event), recorded notably by drusy quartz-filled<br />
fractures (McGill et al. 1993) and pre-ore tombstone-style silicification (Q1; Yeo<br />
et al. 2001b; Mwenifumbo et al., 2004, 2005), are particularly intense in<br />
Athabasca sandstone sequences above or proximal to basement quartzite. The<br />
tombstone silicification <strong>of</strong> the Athabasca Group preserves diagenetic hematite<br />
and dickite (Mwenifumbo et al. 2005) and microbial laminae (Yeo et al. 2005a)<br />
very close to the McArthur River deposit.<br />
Figure 70 - Two end-member sandstone alteration models for egress-type deposits in the eastern<br />
Athabasca Basin (modified from Matthews et al. 1997, Wasyliuk, 2002 and Quirt, 2003). UC =<br />
unconformity, Reg = regolith pr<strong>of</strong>ile grading from red hematitic saprolite down through green<br />
chloritic alteration to fresh basement gneiss, Up-G = upper limit <strong>of</strong> graphite preserved in footwall<br />
alteration zone. Cap = secondary black-red earthy hematite capping ore bodies. Fresh = fresh<br />
basement: Fe-Mg chlorite biotite paragneiss.<br />
Illite-kaolinite-chlorite alteration halos are up to 400 m wide at the base <strong>of</strong> the<br />
sandstone, thousands <strong>of</strong> meters in strike length, and several hundreds <strong>of</strong> meters<br />
vertical extent above deposits (Wasilyuk, 2002, for McArthur River; Kister et al.,<br />
56
________________________________________________________________<br />
2003, for Shea Creek; and Bruneton, 1993, for Cigar Lake). This alteration<br />
typically envelops the main ore-controlling structures, forming plume-shaped or<br />
flattened elongate bell-shaped halos that taper gradually upward from the base <strong>of</strong><br />
the sandstone (Hoeve and Quirt, 1987) Figure 70. Potassium, magnesium and<br />
aluminum ratios are diagnostic <strong>of</strong> the different clay types.<br />
Hydrothermal, ore-related alteration effects are superimposed on pre-existing<br />
alteration assemblages, including the paleo-weathering alteration recorded by<br />
the red-green pr<strong>of</strong>ile below the basal unconformity, and the initial detrital clay<br />
mineralogy that is locally preserved in silicified zones (Mwenifumbo et al., 2005).<br />
This has led to confusion as to which process generated the red-green transition<br />
at the basement-sandstone unconformity. Ore-related white clay alteration is<br />
superimposed on the red hematitic paleo-weathering alteration (McDonald,<br />
1980). Very dark coarse grained hematite alteration forms a cap over ore<br />
deposits such as Cigar Lake (<strong>An</strong>drade 2002).. This very dense, crystalline,<br />
hydrothermal hematite alteration contrasts with the brick red, fine-grained<br />
hematite that is interpreted as a detrital or very early diagenetic mineral, and is<br />
intimately interlayered with clay minerals to form micro-laminae in oncoidal<br />
hematite beds (Yeo et al., 2005a).<br />
Figure 71 - Simplified mineral paragenesis <strong>of</strong> the Paleo- to Mesoproterozoic Athabasca, Thelon<br />
and Kombolgie basins, after Figure 10.21 <strong>of</strong> Kyser et al. (2000). The ages <strong>of</strong> primary uraninite,<br />
the first deposition <strong>of</strong> U in a given deposit, may be different for different deposits, hence U1<br />
(~1500-1600) and U1' (~1350-1400) might both be primary in the Athabasca Basin. Depositional<br />
ages in the Athabasca Group are Zv: U-Pb on volcanic zircon in Wolverine Point Formation, and<br />
Os-Re: primary organic matter in Douglas Formation.<br />
57
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INFRARED ACTIVE ALTERATION MINERALS ATHABASCA BASIN<br />
Figure 72 - The common alteration minerals found in the Athabasca Basin deposits include<br />
dravite (magnesi<strong>of</strong>oitite Mg end member), illite, kaolinite and dickite.<br />
Figure 73 - Chlorites found in the Athabasca<br />
suite. Mg-chlorite and the unique sudoite are<br />
plotted.<br />
58<br />
Figure 74 - Other minerals observed are quartz,<br />
hematite, monazite (REE), dolomite and siderite.
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DISCUSSION<br />
Starting with the PIMA, it took about four hard years to introduce the technology<br />
to the industry. It was very alien to users initially, as most universities do not<br />
teach infrared analytical methods. Those that do, usually treat the subject very<br />
briefly, as most departments do not have expensive infrared instrumentation.<br />
Once applications, case studies, spectral libraries, some simple mineral<br />
identification s<strong>of</strong>tware, and a well-documented training course and manuals were<br />
developed, it became easier to sustain the method.<br />
As more and more companies utilized the technology, word spread via the<br />
"grapevine". Most companies would not cite PIMA analyses in their public<br />
presentations and papers. They all considered reflectance <strong>spectroscopy</strong> their<br />
"secret weapon".<br />
With the introduction <strong>of</strong> the TerraSpec, some <strong>of</strong> the secrecy has dissipated and<br />
companies are more willing to acknowledge the application <strong>of</strong> reflectance<br />
<strong>spectroscopy</strong> to their exploration programs. Additionally, VNIR analysis has been<br />
used for over 10 years and is no longer so exotic.<br />
Spectroscopy is used for <strong>field</strong> and core reconnaissance, core logging, target<br />
generation, vectoring, blast hole logging, and remote sensing ground truth. It has<br />
its biggest successes in epithermal gold systems, porphyry, IOCG, skarns,<br />
kimberlites and unconformity uranium.<br />
Reflectance Spectroscopy has changed the way exploration is done, how core is<br />
targeted, drilled and logged and alteration systems modeled. It has made some<br />
impact on mine metallurgy, grade control and production. It has opened the<br />
important world <strong>of</strong> alteration mineralogy to a rapid, non-invasive, identification <strong>of</strong><br />
alteration minerals in-situ and instantly, in the <strong>field</strong>, in the core shack, on the pit<br />
benches and faces and underground in the tunnels. It has expanded the<br />
geologist’s knowledge about the minerals in alteration systems, their<br />
associations, and the environments in which they form, therefore leading to a<br />
better and more predictive understanding <strong>of</strong> mineral deposits. Now, clays,<br />
phyllosilicates, and carbonates, minerals that have similar physical appearances<br />
and have always been difficult to identify by hand lens, are known in 3, 5, or 10<br />
seconds. This analysis can be in-situ in the <strong>field</strong>, at the outcrop, and/or in the<br />
core shack.<br />
Reflectance <strong>spectroscopy</strong> has been used by all the major and many smaller<br />
companies in some capacity. There are nearly 400 instruments in the industry<br />
between the different manufacturers. Following is a partial list <strong>of</strong> companies who<br />
own or have owned spectrometers and many have more than one (apologies to<br />
those left <strong>of</strong>f the list) : Alamos Gold, Almaden, <strong>An</strong>glo American, <strong>An</strong>glo-Gold-<br />
Ashanti, Barrick, BHP, Balkan Minerals, Battle Mountain, Billiton, Bolnisi,<br />
Buenaventura, Codelco, Collahausi, Cornerstone, CRA, Crystallex, Cyprus, De<br />
Beers, Depromisa, El Dorado, Formicruz, Gencor, GoldCorp, Gold<strong>field</strong>s,<br />
Gryphon Gold, Hecla, Hemlo, Homestake, Hochschilds, Iamgold, Incor, Inmet,<br />
59
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Ivanhoe, Kennecott, Lac, La Coipa, Linear Gold, Mantos Blancos, Mantos Oro,<br />
Metallica, Metallic Ventures, Mineral Mapping, Minera Paramount, Minnova,<br />
Newcrest, Newmont Exploration, Newmont Gold, New Sleeper, Noranda,<br />
Normandy Posieden, North, Nova Gold, Oro Candente, Oro Peru, Penoles,<br />
Phelps Dodge, Placer Dome, QVX, Rio Tinto, Romarco, Santa Fe, Southern<br />
Peru Copper, Teck-Cominco, WMC, and Western States.<br />
Many more companies have either rented instruments or used consultants who<br />
have done spectral analysis for them.<br />
The uranium companies are where <strong>spectroscopy</strong> makes a major contribution to<br />
drill target and core logging <strong>of</strong> alteration to vector to mineralization. The<br />
alteration minerals and clays occur in unique relationships to ore and<br />
<strong>spectroscopy</strong> is the major way to define these relationships and establish<br />
vectors. The companies include Areva, Cameco, Can-Alaska, Forum Uranium,<br />
Jabiru, JNR, Triex, Uranium City, Uravan, Uex. There are over 30 instruments in<br />
Canada and Australia dedicated to this task alone.<br />
DeBeers funded the original PIMA development and then used close to 20<br />
PIMAs to characterize alteration in kimberlite pipes globally. G-10 garnets, as<br />
diamond indicators, have a distinctive chrome feature in the <strong>vis</strong>ible, easily<br />
analyzed by the Terraspec.<br />
The alteration model for Pierina was done with the PIMA. Newmont at<br />
Yanacocha evolved from PIMA core logging into using the Terraspec to<br />
define their alteration and drill taregets. Novagold used the FieldSpec Pro (FR)<br />
at Donlin Creek, as did Barrick at Alta Chicama and Ivanhoe at Oyu Tolgoi. It<br />
goes on with Lac and Barrick in the El Indio belt where they redefined alteration<br />
and mineralization episodes finding major advanced argillic alteration throughout<br />
the belt; Placer Dome logged core at La Coipa. At Valedaro, in Argentina, no<br />
hole was drilled before adjoining holes had been checked with the spectrometer<br />
as they had discovered a unique silica signature associated with gold zones. At<br />
Tres Cruces in Peru, Oro Peru defined mineralized zones and degrees <strong>of</strong><br />
alteration using the presence <strong>of</strong> ammonia in illite or buddingtonite. Noranda and<br />
Rio Tinto use their FR's for remote sensing ground truth, as has Buenaventura,<br />
Newmont, Teck-Cominco, WMC and Barrick..<br />
Perhaps the greatest use for <strong>spectroscopy</strong> is in core logging. One <strong>of</strong> the major<br />
success stories, as mentioned, is in the unconformity uranium deposits where<br />
companies have to drill blind targets through glacial till and sandstone down<br />
through the unconformity, where the ore lies, to the basement. The alteration<br />
mineralogy zoning is very diagnostic relative to proximity to ore. The<br />
spectrometers are the most rapid, economic way to vector to the ore bodies and<br />
define them.<br />
Reflectance <strong>spectroscopy</strong> has become a robust method, routinely used in a wide<br />
variety <strong>of</strong> applications in the industry,<br />
60
________________________________________________________________<br />
Acknowledgements<br />
This paper is dedicated to all those <strong>field</strong> geologists who persevered from PIMA to<br />
Terraspec; who collected thousands <strong>of</strong> spectra and applied their new found<br />
knowledge to better understanding their deposits and alteration systems. I<br />
acknowledge all <strong>of</strong> you for your individual and collective contributions to this<br />
wonderful discipline <strong>of</strong> <strong>field</strong> <strong>spectroscopy</strong>.<br />
A special acknowledgement to Graham Hunt, who gave me the first taste <strong>of</strong><br />
reflectance <strong>spectroscopy</strong> years ago at the U.S. Geological Survey. Also to<br />
Alexander F.H. Goetz, who has not only given me knowledge and opportunity,<br />
but taught me a great deal about instrumentation and was supportive in the<br />
creation <strong>of</strong> the fabulous TerraSpec. <strong>An</strong>d to the Team <strong>of</strong> engineers, scientists,<br />
and technical support people at <strong>An</strong>alytical <strong>Spectral</strong> Devices who created the<br />
Terraspec.<br />
Acknowledgement as well to Terry Cocks <strong>of</strong> Australia, who with his CSIRO<br />
colleagues, created the PIMA, the first innovative step in this mini-revolution.<br />
<strong>An</strong>other special salute to <strong>An</strong>ne Thompson, whose tireless and absolutely top<br />
notch efforts through the years has made reflectance <strong>spectroscopy</strong> an accepted<br />
analytical tool for all those Canadian Juniors doing very grassroots exploration,<br />
pioneers in their own rights.<br />
The reader also is referred to the paper “Alteration Mapping in Exploration:<br />
Application <strong>of</strong> Short-Wave Infrared (SWIR) Spectroscopy”, by <strong>An</strong>ne J.B.<br />
Thompson. Phoebe L. Hauff and Audrey Robitaille, SEG Newsletter, 1999,<br />
Number 39, published by the Society <strong>of</strong> Economic Geologists, Littleton,<br />
Colorado.<br />
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