SWIR reflectance spectroscopy is a very sensitive analytical method for the clay

mineral groups for a number of reasons. The OH and H2O bonds are easily detected
in the SWIR range. SWIR does not identify minerals per se, but rather, in the case
of clays, the octahedral layer configurations of minerals, as these are so well defined
by the OH to cation bonds. The SWIR method is particular good for monitoring and
tracking the subtle changes in those layer configurations. This is especially useful
when evaluating water rock interactions with clays in different environments.

This method allows the determination of such processes as hydrothermal fluid

dissemination through a mineral deposit, ground water channels, paleoweathering
influences, and fluid migration along structural features. As SWIR detects the sub-
lattice changes in a mineral species, it is a more subtle analytical technique then X-
ray diffraction for many applications.

Another major application is the evaluation of industrial clay deposits. SWIR and
PIMA can also be used in the petroleum industry to log drill core.

This section will present an overview of the different common clay mineral groups.

KAOLINITE GROUP
ILLITES
ILLITE/SMECTITES
SMECTITES
CHLORITES

This is an informal summary of the SWIR perspective of clay minerals. Additional

information, references and case studies are available through Spectral
International.

KAOLINITE GROUP

The Kaolinite Group of minerals includes kaolinite, halloysite, dickite, nacrite,

"endellite", allophane, and additional commercial clay types such as ball clay and
flint clay.
Figure 1, above, shows the kaolinite group members.

These are [A] nacrite from the Nayarit hydrothermal deposit in Mexico, [B] dickite
from a porphyry copper breccia pipe in Tombstone, Arizona, [C] the best known
crystalline kaolinite from the Warsaw geode in Indiana, [D] crystalline kaolinite from
a hydrothermal location in France. [E] poorly-crystalline kaolinite from a
paleoweathering profile in Provins, France, and [F] halloysite from the industrial clay
deposit in New Zealand.

Kaolinite is a 1:1 phyllosilicate and an acid pH mineral. It is low temperature from

ambient to ~250C, with dickite and nacrite closer to 285C, and is stable from
about pH 3-8. It is common as a hydrothermal alteration product in many types of
deposits. It can be an acid ground water alteration product of illite.

Spectrally, kaolinite has two very distinctive doublets at 1400 and 2200 nm. The
minima are directly linked to the orientation of different octahedral layer structural
components, and change in intensity and profile as the octahedral layer bonds and
composition vary.
Figure 2 - Georgia and French Kaolinites arranged by decreasing structural order

Changes in crystal structural ordering were observed by clay mineralogists working

in the famous Georgia Kaolinite industrial clay deposits (Lyons and Murray, 1963)
with X-ray diffraction techniques. Their Crystallinity Index has been re-cast with
SWIR spectroscopy to show a gradational change in spectral profile and water
content (Figure 2), which is a manifestation of changes in ordering.

The increasing water content is seen in the 1900nm feature and indicates weakening
of interlayer bonds as a function of disorder and the development of interlayer
spaces that accommodate water and hypothesized development of smectitic layers.

Note in this expanded scale version of Figure 2, below, how the kaolinite doublet in
the 2200nm region softens and broadens from a sharp, defined minimum to a
shoulder as ordering decreases. This change in profile can be mathematically
defined and utilized as an index. It is a function of random and sporadic filling of
metal sites in the octahedral layer of the mineral. Empty and random sites decrease
order and therefore the sharpness of the profile.
Figure 2A - Expanded view of Figure 2.

The change in slope, flagged with the red arrows, can be measured and used as a
crystallinity index.

Mixed Layer Kaolinite/Smectite Clays

The interstratification of kaolinite and smectite is found in many paleoweathering

profiles. The best documented occurrence is in the Paris Basin of France.

The following plot shows a progression from kaolinite-dominated (KSPB95) to

smectite-dominated (KSPB00). The numbers in the file names refer to approximate
percentages of kaolinite. These are estimated from X-Ray Diffraction work on the
samples. Note the changes in the features at 1400nm and 2200nm as the
progression moves from kaolinite with doublets to smectite with single features.
Figure 3 - This figure compiles a progression from high (95%) kaolinite layers [A]
through [B] 90% kaolinite, [C] 80% kaolinite, [D] 75% kaolinite, [E] 55% kaolinite [F]
45% kaolinite, [G] 20% kaolinite, [H] 2% kaolinite plus calcite, to [I] all smectite layers.

ILLITE --> KAOLINITE

A commonly observed phenomenon in mineral deposits with illitic, sericite or phyllic

alteration is the kaolinitization of the illite/mica. Figure 4 shows spectra from a
porphyry copper deposit. The illite, which was probably originally phyllic muscovite,
is now being altered by acid ground water to kaolinite. What is most likely happening
is that layers of 1:1 phyllosilicate configurations are developing within the 2:1 mica--
>illite structure. Therefore, although this is treated here as a discrete mineral phase,
it probably is not discrete. This hypothesis has never been physically tested, as it is
very difficult to separate the secondary clay minerals from each other because they
are very fine grained. X-ray diffraction is usually not sensitive to these changes.
Figure 4 shows illite [A], illite with minor kaolinite (note the profile changes of the
2200nm feature)[B], poorly crystalline kaolinite with minor illite [C] and [D] kaolinite.
The changes in [B] are particularly subtle, but diagnostic of acid ground water flow.

ILLITES

Illites are environmental monitors and show a crystallinity change with temperature.
This can be used to trace illites through an environment and vector towards geologic
and mineralization changes.

Figure 5, below, compiles illites from [A] Morenci, AZ, porphyry copper phyllic zone,
[B] Leadville, CO, base metal veins, [C] Carlin, NV, sediment hosted epithermal gold,
[D] Hog ranch, NV, volcanic hosted disseminated gold, [E] Fithian illite from
sediments in Illinois, and [F] ammonia-bearing illite from black shales above the
Mercur Mine, UT.
Figure 5 - Illites by environment.

Illite will also have different cations substituting into various sites with diagnostic
changes in the spectral profile. In Figure 6, below, spectrum [A] is an
interstratification of illite and smectite with higher aluminum contents in two
octahedral layers, shown by a shift to lower wavelengths (2188nm) of the 2200nm
feature. Contrast this with [B], an illite from a low temperature gold system, which
shows higher aluminum then the average illite (see next section) but less than in [A].
In spectrum [C], NH4 is substituting for potassium and creating an ammonium-illite.
This manifestation is shown in the features flagged with red arrows. When iron
substitutes into the octahedral layer, the features shift to a higher wavelength
(2310nm). This is glauconite, the iron-illite [D].
Figure 6 - Illites by chemistry.

Chemical Variability - Illites

The aluminum content of illites can be estimated from the 2.2m absorption feature,
which shifts relative to the percent aluminum present. There appears to be a deposit-
specific correlation. When illite/"sericite"/muscovite alteration is present, higher
amounts of aluminum are apparently associated with the ore zones. This has also
been documented by Post and Noble (1993) and their data is plotted below against
spectral wavelength values collected from their published samples.

Feature positions for a cross section of muscovites and illites from SPECMIN
range from 2198nm to 2212nm, with the majority falling within 2200-2204nm.

The illites plotted in Figure 7 are from different environments, and from top to bottom
are: [A] Hog Ranch, Nevada, epithermal gold deposit; [B] Chuquicamata, Chile,
porphyry copper; [C] Leadville, Colorado, gold vein system; [D] Cananea, Mexico,
porphyry copper deposit; [E] Round Mountain, Nevada, disseminated gold deposit;
[F, G, H] sedimentary illites from Illinois shales.

The red line is positioned at the minimum for the 2200nm absorption feature. The
hydrothermal samples all line up near 2200nm, with is high alumina - about 35%
Al2O3. The sedimentary illites, however, all show shifts to the higher wavelengths,
indicating less alumina than observed in the hydrothermal varieties.
Figure 7 - Cross section of illites showing a spectral shift from 2198 (top) to 2222nm
(bottom).

Smectite --> Mica Plot

Figure 8 plots a series from smectite ([A] Arizona) through mixed-layer smectite/illite
[B] and illite/smectite [C, D], to epithermal gold illite [E] Hog Ranch, NV, [F] Round
Mountain, NV, to vein illite [G] El Indio, Chile, to phyllic illite in porphyry copper
systems from [H] Silver Bell, Az and Cananea, Mx [I].
Figure 8 Smectite --> Muscovite Spectral Sequence Plot

This is a classic sequence of changing crystallinity and proportional chemistry. The

structures are very similar as are the compositions with like-octahedral layer
configurations. Interlayer positions in smectite are occupied with water and common
cations such as Ca, K, Mg and Na. As order increases and potassium replaces the
water and fills the interlayer sites, illite and then muscovite evolve.

Although it is easy to differentiate the end-members, it is not so easy to distinguish

between near neighbors. This is one of the more common series of minerals
encountered in infrared spectroscopy. It gives the most difficulty in identification.

Note in the plot below how the wavelength position of the 2200nm feature shifts. This
is a function of the aluminum composition of the octahedral layers. As stated, the
structure of the individual members within this series of mineral phases is very
similar. The major differences are ordering and chemistry. The mixed layer
constituents contain the most aluminum [C, D], then the illites from porphyry copper
systems [G, H, I], then the illites from epithermal gold systems [E, F], with smectite
[A] and the smectite dominated Illite/Smectite carrying lesser amounts.
Figure 8A - Expanded view of the 2200 nm region from Figure 8.

The chemical compositions are one way of differentiating the species, but since there
is overlap, it must be done within restricted environments and usually is difficult,
except in generalities, to cross environments of paragenesis.

This underlines the need to understand environments better from a spectral

perspective and also to utilize the concept of site-specific databases.

SMECTITES

Smectites are sensitive to their environment and form at low temperatures (less then
150C), usually in alkaline, neutral conditions. They will reflect the type, amount,
and transit of cation-bearing ground waters through the rock or soil.
Figure 9 - Smectite Group minerals; [A] beidellite-Al, [B] montmorillonite-Al/Mg, [C]
hectorite-Li, [D] nontronite-Fe, [E] iron saponite-Mg/Fe, [F] saponite-Mg, and [G]
sauconite-Zn.

Smectites are a common constituent of soils and occur as a weathering product of

other clays. They are excellent low temperature indicators. In hydrothermal ore
deposits, they occur in the zones of argillic alteration, away from the mineralization.
The exception to this is beidellite, the aluminum species. Beidellite is found near the
ore zones in some low temperature gold and silver deposits.

Saponites are indicators for clay alteration of the serpentines found within kimberlite
pipes.

Nontronite is associated with enriched porphyry copper deposits and found as a

layer under the supergene-enriched ore blanket.

Hectorite is a lithium source and found in playas and evaporitic lakes.

Sauconite is the Zn-smectite. It is found as ore in zinc deposits such as the Skorpion
zinc mine in Namibia

The most notable thing about the SWIR spectra of smectites is the ability to
differentiate the Fe, Mg, Al, Zn and Li cations using the wavelength positions of the
hydroxyl absorption features. By X-Ray diffraction, the conventional method of
identification, this is a time consuming process. SWIR accomplishes it in 30 seconds.
Figure 9 summarizes the smectite group members. These include; [A] beidellite-Al,
[B] montmorillonite-Al/Mg, [C] hectorite-Li, [D] nontronite-Fe, [E] iron saponite-
Mg/Fe, [F] saponite-Mg, and [G] sauconite-Zn

The red line flags aluminum species in the 2200nm region; green the iron species;
cyan the magnesium species, and gold the zinc phase.

CHLORITE GROUP

The chlorite group is large and very complicated. Chlorites are ubiquitous and can
be found in low temperature regimes where they are considered more as clays and
in higher temperature environments associated with porphyry copper, with VMS, with
kimberlites and base metal systems.

Because of the solid solution substitution series that exists within the various chlorite
species, especially with iron, magnesium and aluminum, chlorites respond well to
SWIR analyses and provide valuable information about their environments and
alteration processes.

Figure 10 shows the two chlorite "end members", which are iron-bearing [A] and
magnesium-bearing [B]. Note the different slopes and spectral profiles.

Figure 10 - Iron [A] and Magnesium [B] bearing chlorites.

The changes in the spectra and absorption feature positions are dramatic and, for
the most part, when chlorites are present in perhaps at least 15% amounts, their
species can be determined. The identification between an iron and non-iron chlorite
is helped by the positive slope to the continuum seen in the above plot between
~1400 - 1850nm. There are also diagnostic shifts in the wavelength positions. The
shift in the 2300nm feature indicates iron and magnesium substitution in the
octahedral layers.

Chemical Variability - Chlorite

The following plot in Figure 11 shows a series from magnesium-dominated chlorite

[A] through various chemical combinations of magnesium, iron and aluminum, to the
iron end member [F].

Figure 11 - Mg --> Fe Chlorites

These spectra are from samples archived at the Royal Ontario Museum in Toronto,
and have chemical analyses providing percentages of Mg, Fe, and Al. This data is
available through Spectral International in the SPECMIN reference database. By
overlaying reference spectra from this database, it is usually possible to obtain a
reasonable idea of the composition of the unknown chlorite.