Economic Geology

Vol. 96, 2001, pp. 401–420

Atacamite Inclusions in Rock-Forming Feldspars and Copper-Bearing Smectites from

the Radomiro Tomic Mine, Chile: Copper-Insoluble Mineral Occurrences
GEORGE H BRIMHALL,†
Department of Earth and Planetary Science and the Earth Resource Center, University of California at Berkeley,
Berkeley, California 94720-4767

BEATRIZ LEVI,
Kallforsvägen 8, SE-12432 Bandhagen, Sweden

JAN OLOV NYSTRÖM,

Swedish Museum of Natural History, Box 50007, SE-10405 Stockholm, Sweden

AND ENRIQUE TIDY F.

Exploration Division, CODELCO, Santiago, Chile

Abstract
Recovery of copper from the Radomiro Tomic deposit in Chile employs innovative large-scale hydrometal-
lurgical extraction methods, with sulfuric acid used for heap leaching. Here, we report on improvements in un-
derstanding mineral components of copper oxide ores, which are insoluble in acid leach solutions, in order to
advance leaching technology. Using optical, electron microprobe, X-ray diffraction, energy dispersive spec-
troscopy, and least squares inversion methods, two different occluded mineral occurrences were discovered in
oxide ores, which present two distinct metallurgical challenges for heap leaching but offer important new op-
portunities in process mineralogy. First, in a high chloride to sulfate ratio, feldspar-stable portion of the ore-
body at Radomiro Tomic, disseminated atacamite (Cu4Cl2(OH)6) inclusions, 1 to 8 µm in diameter, occur in
microfractured feldspars and biotites. These account for the acid-insoluble fraction, often as high as 30 percent
of the total contained copper. About 70 percent of the total copper occurs generally as atacamite in cracks,
which upon crushing is exposed along surfaces of the rock fragments and is hence soluble. In contrast, in more
intensely hydrothermally altered, feldspar destructive, weak argillic alteration zones, insoluble copper exists
more probably within the crystal structure of well-crystallized saponitic smectite clays in nonexchangeable, oc-
tahedral crystallographic sites. The two different forms of applied acid-insoluble components are products of
contrasting microchemical environments, one in a reactive potassic alteration gangue and the second in a non-
reactive gangue. In both cases, however, the nature of hydrothermal alteration, though pervasive, was relatively
weak and left intact rock mineral buffers capable of neutralizing acidic and reducing fluids. Hence, the insol-
uble components with respect to the applied sulfuric acid reflect strong wall-rock mineral assemblage control
on the behavior of copper on all scales: the macrofield zonal scale, the microscale of individual crystals in
cracks, and the atomic scale of octahedral sites in the clay structure.
The metallurgical implications of these atacamite microinclusions in rock-forming minerals and structurally
bound copper in smectites are different. In the former case, exposing ore inclusions on fragment surfaces
would require extremely costly grinding to a grain size well below 400 mesh. Secondly, chemical extraction of
microinclusion copper from feldspar host phases would entail high acid consumption, as hydrolysis of feldspars
by chemical reaction with applied acid would occur causing neutralization. In the case of Cu smectites, since
the copper occurs in structurally bound, nonexchangeable sites, processes to remove the copper via ion
exchange or acidic leach cannot work. Alternatives to ion exchange could involve destroying the smectite host
mineral, perhaps by its conversion to kaolinite that may only incorporate copper or other divalent cations in
negligible amounts.

Introduction which has required adding yet a new microscopic focus to

Where the telescope ends, the microscope begins.
Which of the two has the grander view?
Les Miserables by Victor Hugo, Book III, Chapter 3.
TYPICALLY, exploration geologists apply knowledge of rela-
tively large scale crustal and district-scale genetic processes in
the search for ore deposits. However, mining of large-tonnage,
low-grade ores has undergone a technological revolution,
†
Corresponding author: e-mail, brimhall@socrates.berkeley.edu
economic geology that better bridges the scientific descrip-
tion of orebodies with growing demands on mineralogical un-
derstanding applied to metallurgy. Besides a traditional ore
reserve, today’s data base requirements include the distribu-
tion of mineral species in order to correlate the physical,
chemical, and metallurgical behavior of the different types of
ores and gangue with their response to treatment. This data-
base is the primary input in development of performance and
production cost models, which must be optimized as prices
change unpredictably and too often descend to remarkably

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402 BRIMHALL ET AL.
low levels. Translation of ore characterization into practical,
cost-effective advancements in metallurgy is the basis of
process mineralogy, a relatively new discipline which is grow-
ing rapidly in importance and becoming a vital new part of
economic geology. In the heap leaching of oxide copper ores,
recovery of billion dollar capital costs of mine development
and long-term profitability demand simultaneous maximiza-
tion of copper recovery while minimizing acid consumption
and crushing costs. These competing demands require com-
prehensive knowledge of ore mineral distribution of both the
easily recovered and the occluded ore mineral components
that presently are lost.
Porphyry copper deposits present a broad array of geomet-
allurgical problems with respect to process mineralogy. In tra-
ditional sulfide ores, extraction via froth flotation following
fine grinding to the feasible economic limit, ore mineral
grains remain interlocked with gangue to some extent and
lower the concentrate grade by dilution while raising the ore
metal grade of mill tailings. In comparison, acid heap leach
extraction of copper from oxide ores presents its own unique
mineralogical barriers, which we illustrate here with the ex-
amples of two relatively new ore types which can yield a low
copper recovery: atacamite ore and copper clay ore. Our
study was carried out during the development and early pro-
duction phases of the new Radomiro Tomic mine, which is lo-
cated 5 km north of Chuquicamata in the Atacama Desert of
northern Chile (Cuadra and Rojas, 2001). It is largely based
on samples from the upper part of the oxidation zone.
E–W SECTION 10,600N
Box 1 shows provenance of composite samples 1 through
6 for the atacamite study and samples rt-2915
a, b, d and f for the Cu-bearing clays study
Gravels Chrysocolla-atacamite
smectite ore
Mixed ore Enriched ore
FIG. 1. East-west vertical cross section along 10,600 N, looking north through the Radomiro Tomic copper deposit. Ore-
type zones are shown. 200-m grid shows map scale.
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The copper mineralization of Radomiro Tomic is hosted by
a granodioritic to monzogranitic porphyry intrusion, the
Chuqui porphyry (Cuadra and Rojas, 2001), and extends to a
lesser extent upward into the overlying basal alluvial gravels
in certain mineralized paleochannels (Brimhall and Arcuri,
1998). The 150- to 200-m-thick oxidation zone is complex and
difficult to subdivide into well-defined zones because the four
main copper-bearing phases, atacamite, clay, and chrysocolla,
plus Cu wad, occur in highly variable proportions at different
scales. X-ray diffractometry suggests that the polymorph
paratacamite is widespread, associated with atacamite in the
upper part of the oxidation zone, but since it is chemically in-
distinguishible from the latter it is not treated as a separate
mineral in this study. The extent of alteration of the host rock
is also highly variable, from partially altered porphyry with
copper-bearing phases in fractures to an almost completely
degraded rock. The primary minerals are phenocrysts of
quartz, plagioclase, perthitic K feldspar, and biotite (both
phenocrysts and pseudomorphic replacement of hornblende)
in a groundmass of quartz and saccharoidal K feldspar; the
two latter also occur as veinlets.
Geologic Setting
In a schematic vertical cross section (Fig. 1), copper-bearing
clay minerals tend to characterize the upper, very heteroge-
neous part of the oxidation zone, whereas the lower zone gen-
erally is dominated by atacamite mineralization. The copper-
bearing minerals form veinlets and coat fractures. Atacamite
Chrysocolla-smectite ore Atacamite-dominated
(minor atacamite) oxide ore
Primary ore
402
 RADOMIRO TOMIC MINE, CHILE: Cu-INSOLUBLE MINERAL OCCURRENCES 403

also occurs as dissemination and microfractures in feldspar,
and locally, clays constitute an incipient to complete replace-
ment of feldspar. Chrysocolla is preferentially associated with
the clays and gypsum. The clay minerals, which occur in dif-
ferent shades and hues of yellowish-green, are clearly super-
gene. They overprint bluish-green atacamite mineralization
in the upper zone and penetrate deeply into the lower zone
along faults and fractures. On the other hand, there are large
blocks rich in atacamite and poor in clays in the upper zone,
especially in sectors relatively unaffected by fracturing or
faulting. Dissolution and reprecipitation of atacamite in clay-
dominated domains further complicates the picture.
Analytical Strategy
The main purpose of this study was to identify and charac-
terize the mineralogy of ores, which, when leach solutions are
applied, are insoluble in the sulfuric acid solutions. A practi-
cal visual ore classification scheme used at Radomiro Tomic
identifies two ore types that were investigated here: atacamite
ore and copper clay ore. Toward this end, an analytical
method that was both efficient and definitive had to be de-
vised in order to be cost effective and to provide statistically
valid results.
Since the nature of the occluded copper fraction in the
atacamite zones was not at all obvious, we developed an iter-
ative strategy that began with automated gridded point sam-
pling for copper, using the electron microprobe on well-
polished samples. Then, using the results as guides as to which
host minerals to study in more detail, we were able to confirm
the conclusions using high-magnification optical microscopy.
Another strategy using XRD was implemented for the clay min-
erals because they did not take a good polish, thus prohibiting
both electron mircoprobe or polished section petrographic ap-
proaches. It was known from chemical analysis of clay fractions
that the clays could contain considerable amounts of copper.
Thus, other objectives of this study were to identify the clay
minerals, to determine how much copper they contain, and to
establish if the copper in the clay is structurally bound or is due
to the presence of submicroscopic grains of copper minerals.
Samples
Six representative samples of atacamite ore were prepared
from blast hole samples from the 2,915-m bench (Fig. 1, box
1). The numbers of the samples are 1-2915-3, 2-2915-4/5, 3-
2915-3, 4-2915-6/7, 5-2915-6, and 6-2915-7/6 and are re-
ferred to here, respectively, as samples 1 through 6. Chemical
analysis and assaying was done for total copper (Cutotal; range
= 0.29–0.92 wt %), sulfuric acid soluble copper (CuS; 0.19–
0.82 wt %), chloride (Cl; 0.14–0.29 wt %), iron (Fe; 0.55–1.07
wt %), and carbonate (CO3; 0.12–0.47 wt %).
The clay minerals were studied in seven samples; three of
them were collected from the 2,915-m bench near the blast
hole sampling locations in Figure 1. The sample numbers are
RT-2915-A, RT-2915-B, and RT-2915-D; they are clay domi-
nated in spite of the vicinity to the blast hole samples (nos. 1,
2, 4, and 6, respectively), which emphasizes the spatial vari-
ability of the mineralization. Additional samples rich in clay
minerals came from two exploration tunnels shown in Figure
2 (samples RT-13007, RT-13014, and RT-13923) and a drill
core (DDH-3758; 151.9-m level).

E–W SECTION 10,700N

Box 1 shows location of sample DDH-3758 – 151.9m (smectite)

Box 2 shows location of sample RT-13007 (smectite)
Box 3 shows location of samples RT-13014 and RT-13923 (smectite)

Gravels Chrysocolla-atacamite Chrysocolla-smectite ore Atacamite-dominated

smectite ore (minor atacamite) oxide ore

Mixed ore Enriched ore Primary ore

FIG. 2. East-west vertical cross section along 10,700 N, looking north through the Radomiro Tomic copper deposit. 200-
m grid shows map scale.

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404 BRIMHALL ET AL.

Atacamite Ore
Sample preparation
The blast hole samples consist of granular material created
from intact rocks in the drilling process. In order to be able to
prepare mounts for examination by microscopic and micro-
chemical methods that require polishing, we screened each
sample into four different size ranges, using 20-, 100-, and
140-mesh sieves. In this fashion, treatment of grains of about
the same diameter allowed us to make high-quality polished
epoxy grain mounts for use on the electron microprobe.
Without the screen classification step, both large and small
grains would occur together, which would result in overesti-
mation or underestimation of grains of different size. Four
A
separate epoxy plugs of a 2.54-cm diameter were cast, each
containing the same size fraction of all samples.
Polished sections were optically studied for each of the size
fractions. Very few sulfide minerals were identified even
under 400 or 1,000 magnification, disproving the previous as-
sertion that insoluble copper was in the form of sulfides. We
conclude instead that copper sulfide minerals are an insignif-
icant contribution to the acid-insoluble fraction of all of these
samples.
Analytical methods
A Cameca SX-50 electron microprobe at the University of
California, Berkeley, was used to study the samples, numbers
1 to 6, using a beam diameter of about 5 µm and an acceler-
ating voltage of 15 kV with a sample current of 20 nA. The fol- B
lowing elements were analyzed: copper (Cu), iron (Fe), man-
ganese (Mn), oxygen (O), chlorine (Cl), sodium (Na),
potassium (K), aluminum (Al), silicon (Si), magnesium (Mg),
FIG. 3. Histogram of (A) plus 20-mesh and (B) 20- to 100-mesh size sam-
calcium (Ca), and cobalt (Co). Counting times varied with 2, ples categorized by wt percent copper in 5-µm-diam spots by electron mi-
5, or 10 s on peak with an equal time-off peak depending croprobe analysis.
upon the element. For copper, the analytical detection level
is about 0.064 wt percent Cu for a 95 percent confidence
level, 0.049 wt percent Cu for 90 percent, 0.035 wt percent the 1,600 spots analyzed contain copper above the limit of de-
Cu for 80 percent, and 0.022 wt percent for a 60 percent con- tection (0.022 wt % or 220 ppm for a 60% confidence level).
fidence level. For chloride, the limit of detection is about It should be kept in mind that the electron beam is about 5
0.014 wt percent Cl for 95 percent confidence, and 0.010, µm in diameter. Hence, the frequency of copper-bearing
0.008, and 0.005 wt percent for 90, 80, and 60 percent confi- spots implies occurrence in relatively common minerals,
dence levels, respectively. which should be visible using the petrographic microscope
Besides spot analyses of minerals under manual control, we with a high power objective that can discern minerals in ex-
have used the electron microprobe to do approximately 1,600 cess of 2 or 3 µm in size.
point analyses in total on the plus 20-mesh and 20- to 100- In order to interpret the nature of the copper-bearing
mesh screen sizes in the polished plugs under automated con- phase(s), in Figure 4 we plot a series of definitive elements
trol, which allows for 24 h/d use of the instrument. For each (Cu, Fig. 4A; Cl, Fig. 4B; molar Cu/Cl, Fig. 4C) against K, an
of the two groups of analyses, the time required was about 15 element present at different contents in the several dis-
h to do the 12 elements listed above. cernible rock-forming minerals of the host rock. Notice in
Figure 4C that many of the data points fall near a value of 2.0
Electron microprobe results for molar Cu/Cl, which is representative of ideal stoichiomet-
From the group of elements analyzed by electron micro- ric atacamite Cu4Cl2(OH)6 and is shown as a horizontal line
probe, it was possible to discover not only the spots with ele- near the bottom of Figure 4C. We interpret the data to rep-
vated concentrations of copper but to ascertain their mineral- resent microscopic inclusions of atacamite in 60 percent of
ogy as well as that of the minerals hosting them, thereby the analyzed spots. The points with higher Cu/Cl in the dia-
providing necessary guidance for subsequent optical exami- gram correspond to analyses where the Cl was very low and
nation of inclusions in specific rock-forming minerals. In Fig- in part is due to analytical uncertainty in the Cl data. How-
ure 3, we show histograms for the spots analyzed by micro- ever, since chrysocolla has also been found in the samples,
probe on the plus 20-mesh (Fig. 3A) and the 20- to 100-mesh some of the data plotting along the vertical axis might repre-
(Fig. 3B) sets of samples. In both cases, over 60 percent of all sent this mineral.

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 RADOMIRO TOMIC MINE, CHILE: Cu-INSOLUBLE MINERAL OCCURRENCES 405

Analogous diagrams for Ca (Fig. 5A-C), Na (Fig. 6A-C), Si

(Fig. 7A-C), and Al (Fig. 8A-C) show similar patterns for the
microinclusions of atacamite in gangue mineral rock-forming
silicates, further implicating as copper hosts phenocryst pla-
gioclase (Fig. 5), potassium feldspar (Figs. 6 and 7), and mus-
covite (Figs. 7 and 8). Figure 9A-C indicates that most mi-
croinclusions of atacamite occur within host silicates with Fe
contents of 2.2 wt percent or lower, such as Mg-rich biotite in
the potassic alteration zone. The electron microprobe results
provided guidance for high-magnification petrographic exam-
ination of samples for silicate minerals. These studies confirm
A the presence of 1- to 8-µm-diameter microinclusions of ata-
camite in plagioclase (Fig. 10A) and biotite (Fig. 10B).

B A

C
B
FIG. 4. Wt percent (A) Cu, (B) Cl, (C) molar ratio of Cu/Cl, vs. wt per-
cent K in plus 20-mesh size samples. Note that a Cu/Cl molar ratio of 2.0 is
indicative of atacamite as its ideal formula is Cu4Cl2(OH)6.

The identity of the various host minerals containing oc-

cluded copper can be inferred from the multielement probe
data. In Figure 4A, we show the wt percent Cu as a function
of the wt percent K in four different host minerals, all
feldspars, where copper occurs as inclusions. With increasing
K content the minerals are plagioclase, exsolved albite in
perthite, orthoclase, and fine-grained K feldspar in the
groundmass of the porphyry host rock. Notice that the copper
concentration ranges up to 2.5 wt percent. The data form dis- C
cernible groups for each of the inferred host minerals. The
chloride versus K concentrations in wt percent (Fig. 4B) show FIG. 5. Wt percent (A) Cu, (B) chloride, and (C) molar ratio of Cu/Cl (C)
a pattern similar to that in Figure 4A. vs. wt percent Ca.

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406
A
B
C
FIG. 6. Wt percent (A) Cu, (B) chloride, and (C) molar ratio of Cu/Cl (C)
vs. wt percent Na.
Contribution of microscopic atacamite grains
to overall copper
Using composition-volume-density relationships it is possi-
ble to determine the contribution of recognized microscopic
grains of atacamite to the overall copper grade of the samples
studied. The governing relationship between mineral volume,
chemical concentration of Cu in the mineral, and its contri-
bution to the overall copper grade of the sample follows the
method of Brimhall et al. (1984). The Cu contribution in the
rock from each mineral is equal to the product of the con-
centration of Cu in the mineral (in wt %) times the wt percent
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BRIMHALL ET AL.
A
B
C
FIG. 7. Wt percent (A) Cu, (B) chloride, and (C) molar ratio of Cu/Cl (C)
vs. wt percent Si.
of the mineral divided by 100. To determine the wt percent of
each mineral, the volumetric modes must be converted to a
gravimetric basis using mineral density: quartz (2.65 g/cm3),
plagioclase (2.64), alkali feldspar (2.57), biotite (2.90), ata-
camite (3.77). Modal (volumetric) analysis of the plus 20
mesh and 20- to 100-mesh-size fractions were made. We have
computed the distribution of trace copper using least squares
inversion methods and known compositional variation in the
silicate minerals to find a best fit. The modes and calculated
average copper grades for each phase are shown in Table 1 for
the plus 20 mesh samples. The average total contained cop-
per (Cutotal) grade of all six samples is 0.38 wt percent. We offer
an example of the calculated contribution of Cu in plagioclase
406
 RADOMIRO TOMIC MINE, CHILE: Cu-INSOLUBLE MINERAL OCCURRENCES 407

A A

B B

C C

FIG. 8. Wt percent (A) Cu, (B) chloride, and (C) molar ratio of Cu/Cl (C) FIG. 9. Wt percent (A) Cu, (B) chloride, and (C) molar ratio of Cu/Cl (C)
vs. wt percent Al. vs. wt percent Fe.

to the total copper. The mode of plagioclase is 9.7 percent. To
find the wt percent plagioclase in the rock, we multiply the
modal value of 9.7 percent by the ratio of the density of plagi-
olcase to the average density of the minerals present, 2.60 g/cc,
giving a value of 9.85 wt percent plagioclase, slightly larger than
its modal volumetric value. The calculated copper content of
plagioclase from the best-fit regression is 0.26 percent. To find
the contribution of plagioclase to the total copper value, we
multiply the wt percent of plagioclase by the wt percent copper
it contains and divide by 100 since we express the concentra-
tion in percent, yielding 0.026 wt percent copper. Carrying out
this type of calculation for quartz, muscovite, biotite, atacamite,
K feldspar, igneous orthoclase, albite, clays, and chrysocolla,
the total microscopic copper sums to 0.29, including atacamite,
or 0.13 wt percent, excluding atacamite. Therefore, the calcu-
lated microscopically occluded Cu (excluding atacamite) con-
sidering all these minerals is (0.13 / 0.38) * 100 = 34 percent of
total copper of the samples in the plus 20-mesh fraction. The
remaining 66 percent represents the nonmicroscopic Cu, in-
cluding atacamite. The amount of Cu by wt percentage con-
tained in the various minerals as a percentage of total Cu as mi-
croscopic inclusions is quartz (7.7), plagioclase (20), muscovite
(0.35), biotite (3.2), hydrothermal K feldspar (42), igneous or-
thoclase (23), albite (0.85), and clays (2.2), excluding atacamite.
The analogous results for the 20- to 100-mesh samples are
illustrated in Table 2. The average copper grade of all six

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408 BRIMHALL ET AL.

0 10 20 30 40 50µm

A B

FIG. 10. Photomicrograph of disseminated atacamite microinclusions in (A) plagioclase and (B) biotite shown at same
scale.

samples in this size range is 0.50 wt percent Cutotal, which
means the microscopic copper is (0.13/0.50) * 100 = 26 per-
cent of the total copper. Thus, by combining results on the
plus 20- and the 20- to 100-mesh samples, we conclude that
the microscopic copper mineral inclusions contained in other
minerals account for about 30 percent of the total copper in
these samples.
How representative these results are for the other size frac-
tions besides the plus 20- and the 20- to100-mesh size is eas-
ily ascertained. By having screened each of the six samples
into four separate size fractions and studying the two larger
ones more amenable to electron microprobing of intact sur-
faces, we demonstrated that all samples in each of the four
fractions from coarsest to finest showed the typical increase in
total copper with decreasing size by a factor of two to three.
This effect is generally attributed to finer grinding liberating
fracture-controlled mineralization. However, the ratio of acid
soluble copper to total copper (a range of 85–100%) re-
mained roughly constant (within ±5%) over all size ranges.
Hence, we are certain that in all size ranges, these microin-
clusions of atacamite do in fact represent most of the insolu-
ble copper fraction of the samples poor in clays and most of it
(80 wt %) is in rock-forming feldspars.
Copper-Bearing Clay Ore
Sample preparation
The eight samples collected for this part of the study were
examined under a stereomicroscope, and representative por-
tions of different clay domains of various colors were hand-
picked for mineralogical and chemical analysis. The sampled
clay domains include veinlets and fracture coatings, shapeless
microcrystalline aggregates and patches of soaplike appear-
ance, and pseudomorphs after feldspar judging from their
habit. Microfractured inhomogeneous parts with atacamite
and chrysocolla visible under the stereomicroscope were
avoided. The colors of the clay minerals vary in different
shades of green and yellow, to almost white. Before analyzing
the separated clays with X-ray diffraction, a few representa-
tive grains were selected from each separate for microchemi-
cal analysis and crushed to smaller particles by simple pres-
sure (no grinding).
Analytical methods
Twenty-two X-ray diffractograms (Cu radiation; scans from
2° to 65° 2θ) with count data collected at intervals of 0.02° 2θ
for a time of 1.25 s were obtained of seemingly homogeneous

TABLE 1. Modes and Calculated Average Copper Grades for TABLE 2. Modes and Calculated Average Copper Grades for
Each Phase (plus 20 mesh) Each Phase (20–100 mesh)

% Cu in Contribution % Cu in Contribution
Vol mineral Bulk Wt to total Vol mineral Bulk Wt to total
Mineral percent regression density percent Cu (%) Mineral percent regression density percent Cu (%)

Quartz 38 0.03 2.65 38.73 0.012 Quartz 39 0.03 2.65 39.75 0.012
Plagioclase 9.7 0.26 2.64 9.85 0.026 Plagioclase 11 0.32 2.64 11.17 0.036
Muscovite 0.6 0.07 2.8 0.65 0.00046 Muscovite 2.1 0.03 2.8 2.27 0.00068
Biotite 2.2 0.17 2.9 2.45 0.0042 Biotite 1.8 0.67 2.9 2.0 0.013
Atacamite 0.2 57 3.77 0.29 0.16 K feldspar 25 0.13 2.57 24.71 0.032
K feldspar 29 0.19 2.57 28.66 0.054
Igneous
Igneous
orthoclase 13 0.24 2.57 12.85 0.031 orthoclase 11 0.22 2.57 10.87 0.0224
Albite 1.6 0.07 2.62 1.61 0.0011 Albite 5.7 0.11 2.62 5.74 0.0063
Chrysocolla 5.6 0.06 2.2
_____ 4.74 0.0028
_______ Chrysocolla 4.9 0.19 2.2
_____ 4.14 0.0079
_______
2.6 0.13 2.60 0.13

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 RADOMIRO TOMIC MINE, CHILE: Cu-INSOLUBLE MINERAL OCCURRENCES 409

clay mineral domains without visible grains of other phases

under the stereomicroscope. Sixteen of these samples were
rerun from 3° to 16° after ethylene glycol solvation in order
to check the swelling character of the clays. In addition, 16
determinations of green and blue Cu minerals, clay with relict
feldspar, and illite were made. The X-ray diffraction data for
the clays were interpreted based on information in Thorez
(1976), Bailey (1991), and the International Centre for Dif-
fraction Data (1993). A total number of 183 chemical analy-
ses were made with energy dispersive spectroscopy, using a
scanning electron microscope in different domains, 141 of
them in clay minerals, 11 in Cu chlorides and silicates, and 14
in relict feldspar, illite, biotite, and apatite. Fifteen analyses
were discarded because the analyzed grain contained more
than one phase. This method gives less accurate data than
analysis with electron microprobe, especially with regard to
light elements. However, Cu is sufficiently well resolved that
the results serve a useful purpose of internal comparisons.
Both the X-ray diffractometry and energy dispersive spec-
trometry were made at the Swedish Museum of Natural His-
tory, Stockholm.

Copper-Bearing Smectites
Smectite composition
Chemically, the analyzed clay minerals from Radomiro
Tomic are rather uniform with respect to Si, Mg, Ca, Na, and
K but highly variable in Al, Fe, and Cu (Table 3). They are
characterized by high Si contents (SiO2 = 48–57 wt %), mod-
erate to very high Al (Al2O3 = 10–36 wt %), low to moderate
Fe (Fe, for comparative purposes given as FeO = 1–12 wt %;
however, most of the Fe is probably trivalent), very low to
moderate Mg, Ca, Na, and K (MgO = 0.0–2.6, CaO = 0.0–2.3,
Na2O = 0.0–2.5, and K2O = 0.0–1.4 wt %). Copper varies
from 0.1 to 23.0 wt percent (Fig. 11), and Cl is either absent
(samples DDH-3758, RT-13014, and RT-13923) or present in
small amounts, usually less than 0.4 wt percent; in one sam-
ple up to 0.7 wt percent). Some differences in chemical com-
position can be related to site. Generally, the veinlets are
richer in Cu than patches in the rock, which in their turn tend
to have higher Cu contents than pseudomorphs after feldspar.
In addition, domains of stronger color are usually richer in Cu
than those of paler shades. Veinlets are also richer in Fe and
poorer in Al and Mg than the pseudomorphs after feldspar.
In a plot of interlayer cation total (Ca + Na + K) versus Si,
the high Si values (between 8.5 and 10 based on 28 oxygens)
of the clay minerals identify them as smectites (Fig. 12).
Chlorites normally have values less than 6.25, and mixed-layer
interstratified smectite-chlorite phases plot between 6.25 and
8 (cf. Bettison and Schiffman, 1988; Schmidt and Robinson,
1997, and references therein). It cannot be excluded that
analyses with Si values in the 8 to 9 range represent inter-
stratified phases. These analyses correspond to Cu-poor
smectites replacing feldspar. However, all the clay minerals in FIG. 11. Distribution of copper in different domains of smectite in sam-
samples DDH-3758 and RT-13007 are pure smectites, even ples from the oxidation zone of Radomiro Tomic (wt % Cu based on sum of
those in feldspar sites, like the large majority of Cu-bearing oxides recalculated to a total of 88 wt %). Each square represents one analy-
smectites in the other samples (Fig. 12). Other compositional sis. The letters V, R, or F stand for smectite in veinlets (and coated planes),
rock (= patches in rock), and pseudomorphs after feldspar, respectively, fol-
features consistent with a smectitic nature are the moderately lowed by a second letter indicating color: a = apple-green, d = dull olive-
high sums for the interlayer cations (Ca + Na + K) and the green, g = unspecified yellowish-green to green, p = pistachio-green, w =
rather high Ca values for the Cu-bearing smectites (Fig. 12, waxy olive-green, and y = yellow shades.

0361-0128/98/000/000-00 $6.00 409

 TABLE 3. Representative Chemical Analyses (Energy Dispersive Spectroscopy) of Smectites from the Oxidation Zone of Radomiro Tomic
410
Sample DDH-3758; 151.9 m RT-2915-A RT-2915-B

Site Vg2 Vg1 Vg3 F Vy Rp

Analysis 24 29 33 Average Range 4 13 16 Average Range 61 Average Range 52 Average Range 7 Range 7 11 18 Average Range
(19) (19) (21) (21) (5) (5) (6) (6) (2) (21) (21)

SiO2 (wt %) 53.66 51.04 53.10 53.44 49.5–56.4 54.19 54.61 54.04 54.58 53.4–55.6 51.22 52.50 51.2–53.7 55.70 55.57 55.2–55.8 53.79 51.3–53.8 51.77 53.47 53.31 53.78 50.8–56.4
Al2O3 19.31 14.75 17.63 17.79 12.5–20.1 13.93 17.61 16.68 16.92 13.9–18.1 22.32 22.66 22.1–23.5 22.20 22.88 21.6–23.8 17.18 17.2–23.1 28.84 22.54 19.92 23.04 19.3–29.6

0361-0128/98/000/000-00 $6.00
FeO 8.05 4.68 6.31 6.73 3.4–11.9 7.94 9.10 8.60 8.79 7.8–10.7 8.79 7.20 5.3–8.8 5.02 4.49 3.6–5.4 10.39 8.1–10.4 3.76 6.43 7.50 5.43 3.8–7.7
MgO 1.72 0.80 1.00 1.14 0.7–1.7 1.28 1.34 1.34 1.27 0.8–1.7 1.62 1.56 1.4–1.7 1.74 1.68 1.5–2.0 0.00 0.0–0.8 0.31 1.03 1.38 1.28 0.3–1.8
CaO 1.03 0.94 0.97 1.03 0.8–1.3 1.25 1.02 1.17 1.13 0.9–1.3 1.13 1.19 1.0–1.4 1.14 1.14 1.1–1.2 0.15 0.0–0.2 0.78 1.49 1.60 1.35 0.7–2.3
Na2O 0.08 0.81 0.37 0.40 0.0–1.0 0.66 0.34 0.53 0.30 0.0–0.7 0.23 0.11 0.0–0.3 0.18 0.21 0.0–0.7 2.48 2.0–2.5 1.08 0.81 0.90 1.14 0.3–2.3
K2O 0.75 0.72 0.73 0.59 0.3–1.2 0.20 0.53 0.28 0.39 0.1–1.1 0.12 0.28 0.1–0.7 0.28 0.22 0.2–0.3 0.27 0.3–0.5 0.08 0.35 0.45 0.21 0.1–0.7
CuO 3.40 14.27 7.89 6.87 3.2–14.3 8.54 3.47 5.36 4.62 3.2–8.5 2.57 2.50 2.3–2.7 1.73 1.81 1.7–2.0 3.75 2.3–3.8 1.39 1.88 2.95 1.76 1.3 –3.0
C1 0.00 0.00 0.00 0.00 0.0–0.0 0.00 0.07 0.00 0.02 0.0–0.1 0.00 0.00 0.0–0.0 0.00 0.00 0.0–0.0 0.44 0.3–0.4 nd nd 0.59 0.36 0.0–0.7
Sum 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00
Cu 2.72 11.40 6.31 5.49 2.5–11.4 6.82 2.77 4.28 3.69 2.5–6.8 2.05 2.00 1.8–2.2 1.38 1.45 1.3–1.6 3.00 1.8–3.0 1.11 1.50 2.35 1.41 1.0–2.4

At. proportion based on 22 oxygens

Si 7.62 7.68 7.69 7.70 7.94 7.78 7.78 7.82 7.26 7.36 7.64 7.60 7.77 7.07 7.46 7.55 7.45
Al(IV) 0.38 0.32 0.31 0.33 0.06 0.22 0.22 0.18 0.74 0.64 0.36 0.40 0.23 0.93 0.54 0.45 0.55
Σ(IV) 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00

Al(VI) 2.85 2.29 2.70 2.71 2.35 2.74 2.61 2.68 3.00 3.11 3.23 3.29 2.70 3.71 3.16 2.88 3.21
Fe 0.96 0.59 0.76 0.81 0.97 1.08 1.04 1.05 1.04 0.85 0.58 0.51 1.26 0.43 0.75 0.89 0.63
Mg 0.36 0.18 0.22 0.24 0.28 0.28 0.29 0.27 0.34 0.33 0.36 0.34 0.00 0.06 0.21 0.29 0.26

410
Cu 0.37 1.62 0.86 0.75 0.95 0.37 0.58 0.50 0.28 0.27 0.18 0.19 0.41 0.14 0.20 0.32 0.19
Σ(VI) 4.53 4.68 4.54 4.52 4.55 4.49 4.52 4.50 4.66 4.55 4.35 4.34 4.37 4.35 4.33 4.38 4.29
BRIMHALL ET AL.

Ca 0.16 0.15 0.15 0.16 0.20 0.16 0.18 0.17 0.17 0.18 0.17 0.17 0.02 0.11 0.22 0.24 0.20
Na 0.02 0.23 0.10 0.11 0.19 0.09 0.15 0.08 0.06 0.03 0.05 0.06 0.69 0.29 0.22 0.25 0.31
K 0.14 0.14 0.13 0.11 0.04 0.10 0.05 0.07 0.02 0.05 0.05 0.04 0.05 0.01 0.06 0.08 0.04

At. proportion based on 28 oxygens

Si 9.69 9.77 9.78 9.80 10.11 9.91 9.90 9.95 9.24 9.37 9.73 9.68 9.89 9.00 9.49 9.61 9.49
Al 4.11 3.33 3.83 3.84 3.06 3.77 3.60 3.64 4.75 4.77 4.57 4.70 3.73 5.91 4.72 4.23 4.79
Fe 1.22 0.75 0.97 1.03 1.24 1.38 1.32 1.34 1.33 1.08 0.73 0.65 1.60 0.55 0.95 1.13 0.80
Mg 0.46 0.23 0.28 0.31 0.36 0.36 0.37 0.34 0.44 0.42 0.45 0.44 0.00 0.08 0.27 0.37 0.34
Cu 0.46 2.06 1.10 0.96 1.20 0.48 0.74 0.64 0.35 0.34 0.23 0.24 0.52 0.18 0.25 0.40 0.24
Ca 0.20 0.19 0.19 0.20 0.25 0.20 0.23 0.22 0.22 0.23 0.21 0.21 0.03 0.14 0.28 0.31 0.26
Na 0.03 0.30 0.13 0.14 0.24 0.12 0.19 0.11 0.08 0.04 0.06 0.07 0.88 0.36 0.28 0.31 0.39
K 0.17 0.18 0.17 0.14 0.05 0.12 0.07 0.09 0.03 0.06 0.06 0.05 0.06 0.02 0.08 0.10 0.05

Σ inter-
layer 0.40 0.67 0.49 0.49 0.53 0.44 0.49 0.42 0.33 0.33 0.34 0.33 0.98 0.53 0.64 0.73 0.70
Σ noninter-
layer 15.95 16.14 15.96 15.94 15.97 15.89 15.94 15.91 16.11 15.97 15.71 15.70 15.74 15.71 15.69 15.75 15.66

Notes: The letters V, R, and F stand for smectite in veinlets (and coated planes), rock (= patches in rock), and pseudomorphs after feldspar, respectively, followed by a second letter indicating color: g = unspeci-
fied yellowish-green to green, a = apple-green, p = pistachio-green, d = dull olive-green, w = waxy olive-green, and y = yellow shades
Number of analyses averaged in parentheses; sum of oxides recalculated to a total of 88 wt % (excluding Cl); Al(IV) and Al(VI) correspond to Al in tetrahedral and octahedral position, respectively; Σ(VI) values
include Cu; Σ interlayer = sum of interlayer cations (Ca + Na + K) and Σ noninterlayer = sum of noninterlayer cations, including Cu (Si + Al + Fe + Mg + Cu)
 TABLE 3. (Cont.)

Sample RT-2915-B RT-2915-D RT-13007

Site Ra Rd Rw Ry Rg Ry Va

Analysis 60 61 Average Range 32 38 Average Range 45 Average Range 57 Average Range 6 Range 2 8 9 Average Range
(7) (7) (10) (10) (6) (6) (6) (6) (2) (5) (5)

SiO2 (wt %) 55.01 55.05 55.94 55.0–57.1 52.37 51.58 52.20 50.8–53.4 56.68 56.40 54.8–57.1 55.03 54.96 54.2–55.9 50.57 50.6–53.3 51.59 56.70 53.09 55.14 53.1–56.7
A12O3 20.95 22.15 19.67 17.1–22.2 27.21 29.89 28.88 26.9–31.4 20.57 21.67 20.3–24.2 25.43 24.90 23.5–25.9 29.39 27.4–29.4 29.58 19.28 16.92 19.52 16.9–22.2

0361-0128/98/000/000-00 $6.00
FeO 5.30 4.87 5.83 4.9–7.4 4.90 3.33 3.72 2.7–4.9 4.20 3.84 3.0–4.8 1.26 2.13 1.3–4.0 4.99 2.9–5.0 1.92 5.50 9.88 6.38 4.7–9.9
Mgo 1.76 1.59 1.85 1.6–2.1 0.30 0.64 0.50 0.0–1.1 2.56 2.31 1.9–2.6 1.65 1.56 1.0–1.9 0.32 0.3–0.3 1.43 2.30 1.52 1.75 1.4–2.3
CaO 1.28 1.22 1.33 1.2–1.4 0.87 0.72 0.78 0.5–1.0 1.32 1.21 0.9–1.4 1.41 1.25 0.9–1.4 0.86 0.9–1.4 1.11 0.85 1.33 1.16 0.9–1.4
Na2O 1.63 1.64 1.75 1.4–2.5 0.33 0.25 0.33 0.0–0.9 1.55 1.46 1.3–1.6 1.98 1.68 1.3–2.0 0.14 0.1–0.7 0.90 1.97 1.44 1.71 1.4–2.0
K2O 0.13 0.12 0.14 0.1–0.3 0.23 0.23 0.17 0.1–0.3 0.12 0.18 0.1–0.4 0.70 0.97 0.5–1.4 0.12 0.1–0.4 0.45 0.21 0.12 0.13 0.1–0.2
CuO 1.94 1.36 1.49 1.3–1.9 1.79 1.36 1.43 1.1–1.8 0.99 0.92 0.7–1.1 0.53 0.54 0.1–0.9 1.61 1.6–1.7 1.01 1.18 3.72 2.21 1.2–3.7
Cl 0.50 0.42 0.43 0.2–0.6 0.15 0.06 0.16 0.0–0.3 0.30 0.38 0.2–0.6 0.57 0.40 0.3–0.6 0.03 0.0–0.4 0.31 0.10 0.48 0.30 0.1–0.5
Sum 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00
Cu 1.55 1.09 1.19 1.1–1.6 1.43 1.09 1.14 0.9–1.5 0.79 0.74 0.6–0.9 0.43 0.43 0.1–0.7 1.29 1.3–1.3 0.81 0.94 2.97 1.77 0.9–3.0

At. proportion based on 22 oxygens

Si 7.63 7.58 7.76 7.19 7.01 7.10 7.75 7.69 7.53 7.46 6.95 6.99 7.83 7.67 7.71
Al(IV) 0.37 0.42 0.24 0.81 0.99 0.90 0.25 0.31 0.56 0.54 1.05 1.01 0.17 0.33 0.29
Σ(IV) 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00

Al(VI) 3.05 3.18 2.97 3.60 3.79 3.74 3.07 3.18 3.49 3.45 3.71 3.72 2.96 2.55 2.92
Fe 0.61 0.56 0.68 0.56 0.38 0.42 0.48 0.44 0.14 0.24 0.57 0.22 0.64 1.19 0.75
Mg 0.36 0.33 0.38 0.06 0.13 0.10 0.52 0.47 0.33 0.32 0.07 0.29 0.47 0.33 0.36

411
Cu 0.20 0.14 0.16 0.19 0.14 0.15 0.10 0.09 0.05 0.06 0.17 0.10 0.12 0.41 0.24
Σ(VI) 4.24 4.21 4.19 4.41 4.44 4.41 4.18 4.18 4.01 4.06 4.52 4.33 4.20 4.47 4.27

Ca 0.19 0.18 0.20 0.13 0.10 0.11 0.19 0.18 0.20 0.18 0.13 0.16 0.13 0.21 0.17
Na 0.44 0.44 0.47 0.09 0.07 0.09 0.41 0.39 0.52 0.44 0.04 0.24 0.53 0.40 0.46
K 0.02 0.02 0.03 0.04 0.04 0.03 0.02 0.03 0.12 0.17 0.02 0.08 0.04 0.02 0.02

At. proportion based on 28 oxygens

Si 9.71 9.65 9.87 9.16 8.92 9.04 9.87 9.79 9.46 9.50 8.84 8.90 9.96 9.76 9.81
Al 4.36 4.58 4.09 5.61 6.09 5.90 4.22 4.43 5.16 5.07 6.06 6.02 3.99 3.67 4.09
Fe 0.78 0.71 0.86 0.72 0.48 0.54 0.61 0.56 0.18 0.31 0.73 0.28 0.81 1.52 0.95
Mg 0.46 0.42 0.49 0.08 0.16 0.13 0.66 0.60 0.42 0.40 0.08 0.37 0.60 0.42 0.46
Cu 0.26 0.18 0.20 0.24 0.18 0.19 0.13 0.12 0.07 0.07 0.21 0.13 0.16 0.52 0.30
Ca 0.24 0.23 0.25 0.16 0.13 0.15 0.25 0.23 0.26 0.23 0.16 0.20 0.16 0.26 0.22
Na 0.56 0.56 0.60 0.11 0.08 0.11 0.52 0.49 0.66 0.56 0.05 0.30 0.67 0.51 0.59
RADOMIRO TOMIC MINE, CHILE: Cu-INSOLUBLE MINERAL OCCURRENCES

K 0.03 0.03 0.03 0.05 0.05 0.04 0.03 0.04 0.15 0.21 0.03 0.10 0.05 0.03 0.03

Σ inter-
layer 0.83 0.81 0.88 0.33 0.27 0.29 0.80 0.76 1.07 1.01 0.24 0.61 0.88 0.80 0.84
Σ noninter-
layer 15.57 15.54 15.51 15.80 15.84 15.79 15.50 15.50 15.29 15.35 15.93 15.69 15.52 15.88 15.62
411
 TABLE 3. (Cont.)
412
Sample RT-13007 RT-13014 RT-13923

Site Vy R F Vg Vy F F

Analysis 4 5 Average Range 16 Range 14 Range 9 15 16 17 Average Range 2 3 Average Range 7 Range 7 Average Range
(5) (5) (2) (3) (10) (10) (4) (4) (2) (5) (5)

SiO2 (wt %) 53.55 56.01 54.74 53.6–56.0 56.04 56.0–56.5 54.50 53.8–54.5 43.66 48.98 48.85 49.98 48.61 43.7–50.5 49.43 52.32 51.05 49.4–52.3 51.00 48.9–51.0 52.04 50.34 47.9–52.0
A12O3 18.65 20.97 19.86 18.7–21.0 24.10 24.1–26.7 25.19 25.2–25.6 9.55 17.65 12.41 24.77 18.74 9.6–24.8 15.91 28.97 24.96 15.9–29.0 32.23 32.2–33.5 24.57 30.53 24.6–35.5

0361-0128/98/000/000-00 $6.00
FeO 7.85 4.56 6.27 4.7–7.9 2.17 0.8–2.2 1.44 1.4–1.7 3.03 7.57 4.45 8.77 7.41 3.0–11.3 3.36 4.49 4.88 3.4–6.0 2.28 1.9–2.3 5.86 3.92 2.2–5.9
MgO 1.68 2.22 2.06 1.7–2.3 1.79 0.9–1.8 1.78 1.8–1.9 0.61 0.46 0.20 0.66 0.62 0.0–1.5 0.72 0.38 0.27 0.0–0.7 0.99 1.0–1.0 1.67 0.69 0.0–1.7
CaO 1.48 1.13 1.31 1.0–1.5 1.16 0.8–1.2 1.59 1.3–1.6 0.98 0.70 1.41 0.46 0.78 0.4–1.4 0.75 0.30 0.48 0.3–0.8 0.50 0.4–0.5 0.58 0.43 0.3–0.6
Na2O 2.11 2.00 1.92 1.7–2.1 1.41 1.4–1.5 1.97 1.9–2.3 1.23 0.66 1.49 0.00 0.68 0.0–1.5 1.31 0.00 0.33 0.0–1.3 0.19 0.2–0.3 0.73 0.20 0.0–0.7
K2O 0.04 0.10 0.09 0.0–0.2 0.15 0.2–0.2 0.36 0.4–0.6 0.19 0.22 0.42 0.11 0.26 0.1–0.5 0.21 0.08 0.18 0.1–0.2 0.18 0.2–0.2 1.16 0.67 0.2–1.2
CuO 2.64 1.01 1.74 1.0–2.6 1.18 0.6–1.2 1.16 1.0–1.3 28.75 11.76 18.78 3.25 10.89 3.3–28.8 16.32 1.46 5.85 1.5–16.3 0.64 0.6–0.8 1.41 1.21 0.9–1.8
Cl 0.38 0.37 0.40 0.3–0.6 0.11 0.1–0.2 0.38 0.3–0.5 0.06 0.00 0.00 0.00 0.01 0.0–0.1 0.00 0.00 0.00 0.0–0.0 0.00 0.0–00 0.00 0.00 0.0–0.0
Sum 88.00 88.00 8800 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00
Cu 2.11 0.80 1.39 0.8–2.1 0.95 0.4–1.0 0.93 0.8–1.1 22.97 9.39 15.00 2.59 8.70 2.6–23.0 13.04 1.17 4.68 1.1–13.0 0.51 0.5–0.6 1.13 0.97 0.7–1.5

At. proportion based on 22 oxygens

Si 7.61 7.69 7.64 7.57 7.40 7.29 7.35 7.62 7.09 7.26 7.48 7.12 7.20 6.85 7.24 6.88
Al(IV) 0.39 0.31 0.36 0.43 0.60 0.71 0.65 0.38 0.91 0.74 0.52 0.88 0.80 1.15 0.76 1.12
Σ(IV) 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00

Al(VI) 2.73 3.09 2.91 3.41 3.43 1.17 2.47 1.90 3.23 2.53 2.32 3.77 3.32 3.96 3.28 3.80
Fe 0.93 0.52 0.73 0.25 0.16 0.42 0.95 0.58 1.04 0.92 0.42 0.51 0.57 0.26 0.68 0.45
Mg 0.36 0.46 0.43 0.36 0.36 0.15 0.10 0.05 0.14 0.14 0.16 0.08 0.06 0.20 0.35 0.14

412
Cu 0.28 0.10 0.18 0.12 0.12 3.63 1.33 2.21 0.35 1.27 1.87 0.15 0.65 0.07 0.15 0.13
Σ(VI) 4.31 4.17 4.26 4.14 4.07 5.37 4.86 4.74 4.76 4.85 4.77 4.51 4.60 4.48 4.45 4.51
BRIMHALL ET AL.

Ca 0.23 0.17 0.20 0.17 0.23 0.18 0.11 0.23 0.07 0.13 0.12 0.04 0.07 0.07 0.09 0.06
Na 0.58 0.53 0.52 0.37 0.52 0.40 0.19 0.45 0.00 0.20 0.38 0.00 0.10 0.05 0.20 0.05
K 0.01 0.02 0.02 0.03 0.06 0.04 0.04 0.08 0.02 0.05 0.04 0.01 0.03 0.03 0.21 0.12

At. proportion based on 28 oxygens

Si 9.69 9.79 9.73 9.64 9.41 9.28 9.36 9.70 9.02 9.24 9.52 9.06 9.17 8.72 9.22 8.76
Al 3.98 4.32 4.16 4.89 5.13 2.39 3.97 2.90 5.27 4.16 3.61 5.91 5.24 6.50 5.13 6.25
Fe 1.19 0.67 0.93 0.31 0.21 0.54 1.21 0.74 1.32 1.17 0.54 0.65 0.73 0.33 0.87 0.57
Mg 0.45 0.58 0.55 0.46 0.46 0.19 0.13 0.06 0.18 0.17 0.21 0.10 0.08 0.25 0.44 0.18
Cu 0.36 0.13 0.23 0.15 0.15 4.62 1.70 2.82 0.44 1.62 2.37 0.19 0.83 0.08 0.19 0.16
Ca 0.29 0.21 0.25 0.21 0.29 0.22 0.14 0.30 0.09 0.16 0.15 0.06 0.09 0.09 0.11 0.08
Na 0.74 0.68 0.66 0.47 0.66 0.51 0.24 0.57 0.00 0.26 0.49 0.00 0.12 0.06 0.25 0.07
K 0.01 0.02 0.02 0.03 0.08 0.05 0.05 0.11 0.02 0.06 0.05 0.02 0.04 0.04 0.26 0.15
Σ inter-
layer 1.04 0.91 0.93 0.72 1.03 0.78 0.44 0.98 0.11 0.48 0.70 0.07 0.26 0.19 0.62 0.30
Σ noninter-
layer 15.66 15.49 15.60 15.45 15.36 17.02 16.37 16.21 16.24 16.36 16.25 15.92 16.04 15.88 15.85 15.92
 RADOMIRO TOMIC MINE, CHILE: Cu-INSOLUBLE MINERAL OCCURRENCES 413

FIG. 12. Plots of total interlayer cations (Ca + Na + K) vs. Si for smectites from Radomiro Tomic (at. proportions based
on 28 oxygens). Boundaries between the fields of chlorite (Chl), mixed-layer smectite-chlorite (S-C), and smectite (Smt) are
given in A. See Figure 11 for smectite abbreviations.

Table 3; cf. Schmidt and Robinson, 1997). Also, in this case

the exceptions are found among phases replacing feldspar.
A plot of total noninterlayer cations (Si + Al + Fe + Mg)
against total Al cations (Fig. 13; Schiffman and Fridleifsson,
1991) shows that the smectites rich in Al occupy a field char-
acteristic of dioctahedral smectites, i.e., the montmorillonite
subgroup (Fig. 13A). Smectites containing less Al define a di-
vergent trend toward anomalous compositions. Two samples
with Cu-rich smectites, DDH-3758 and RT-13014, are largely
responsible for the divergent trend (Fig. 13C and E), which
disappears if Cu is treated as a noninterlayer cation. Now, the
smectites with less Al define a new trend—toward the field of
trioctahedral smectites, i.e., the saponite subgroup (Fig. 13B,
D, and F).
The sum of cations in octahedral position Σ(VI) also gives
structural information. Theoretically, the value should be 4
for dioctahedral and 6 for trioctahedral phases (based on 22
oxygens). Table 3 shows that the analyzed smectites have
Σ(VI) values in the range 4 to 4.7 if Cu is included (up to 4.9
or more for sample RT-13014). If Cu would not be taken into
account, then too low values (down to <2) are obtained for
analyses with considerable to high Cu. This indicates that the
Cu-poor smectites are dominantly dioctahedral (montmoril-
lonites) and supports the trend toward a trioctahedral,
saponitic character for Cu-rich varieties.
X-ray diffraction data
The classification as smectite based on chemistry is sup-
FIG. 13. Plots of total noninterlayer cations vs. total Al cations for smec-
ported by the X-ray diffraction patterns. The (001) reflection tites from Radomiro Tomic (at. proportions based on 28 oxygens). The dia-
expands from values less than 15.5 Å (5.7° 2θ) for air-dried grams on the left side (A, C, and E) exclude Cu and those on the right side
material to ca. 17 Å (5.2° 2θ) after ethylene glycol solvation, (B, D, and F) include Cu as a noninterlayer cation. The labels Chlorite, Tri-
generally with appearance of a weak harmonic (002) reflec- octahedral smectite, and Di–octahedral smectite in (A) indicate the
approximative positions of the respective fields (the label of the latter is
tion at ca. 8.5 Å (10.4° 2θ; Table 4, Fig. 14; Thorez, 1976). shifted to the right). See Figure 11 for smectite abbreviations.
The rather low width at half-peak height/peak height ratios
for the (001) reflection in air-dried preparations suggests that
the smectites are well crystallized. The X-ray patterns are

0361-0128/98/000/000-00 $6.00 413

414 BRIMHALL ET AL.

similar to those of dioctahedral smectites (montmorillonites)

14
100

80
I
Glycol
Feldspar pseudom., F
Pale yellow to white given in the literature (International Centre for Diffraction

8.5
17.1

7.3
dÅ
Data, 1993). The (060) reflection for the analyzed smectites
has values in the range 1.485 to 1.498 Å (Fig. 15), which is
RT-13923

well below the limit of 1.52 for the dioctahedral subgroup

91
100

86
15
96
42
11
7
I
1.0 ± 0.3

Dry (Thorez, 1976). In spite of being dioctahedral, a trend toward

1.488
0.86
0.05

4.47
3.58
3.12
2.57
dÅ

15.5
12.9

7.3
a trioctahedral character can be discerned—the d-spacing for
the (060) reflection increases with the Cu content (Fig. 15).

12
100

27
TABLE 4. Peak Positions (d Å = value in Ångstrom) and Intensities (I) for Representative X-ray Diffractograms of Smectites from Radomiro Tomic

This trend is defined by the smectites with considerable to

I
Glycol
Feldspar pseudom., F
Pale yellow to white

high contents of Cu that occur in veinlets, and it coincides

8.5
17.4

7.2
dÅ

with the conclusions based on chemistry.

Two distinct peaks of considerable intensity, at ca. 7.3 Å
55
100

38
9
3.58 42
3.12 29
6
1.491 5
I
0.6 ± 0.1

(12.1° 2θ) and 3.6 Å (24.7° 2θ; Table 4, Fig. 14), pose a prob-
Dry

lem. They correspond to the (002) and (004) reflections, re-

4.47

2.57
0.38
0.05

dÅ

15.5
13.0

7.3

spectively, and are present in all the samples except DDH-

RT-13014

3758 and RT-13007. The existence of these peaks and a rather

100

17
I
Glycol

high value of the ratio between the intensities of the (002)

and (001) reflections (= 7/14 Å; Table 4, Fig. 14) might be
17.4

7.2
dÅ
Yellowish green

taken as evidence of mixed-layer smectite-chlorite phases (cf.

Veinlet, Vg

Schmidt and Robinson, 1997), in contradiction to the conclu-

92

45
4.48 100
51
40
49
1.498 29
I
8.7 ± 6.1

Dry

sions based on chemistry. The symmetry of the (001) reflec-

0.48
0.06

3.59
3.12
2.57

tion in the glycolated runs (Fig. 14) also argues against inter-
dÅ

16.0

7.3

stratification with chlorite (Thorez, 1976). The 7.3 Å peak

17

cannot be caused by a discrete chlorite phase or presence of

100
I
Glycol

kaolinite. Presence of chlorite and/or kaolinite would have re-

8.5
17.0
dÅ

sulted in more than one population among the chemically an-

alyzed grains of a clay domain and not give relatively homo-
RT-13007

Apple-green
Veinlet, Va

76
64

100
10
52
37
23

geneous compositions of high Si content. The problematic 7.3

I
1.8 ± 0.9

Dry

and 3.6 Å peaks are unrelated to the Cu (and Fe) content of

1.494
4.49
3.59
3.09
2.58
0.00
0.05

dÅ

15.0
13.0

the smectites; they appear in smectites rich as well as poor in

Cu (Table 4, Fig. 14). The effect of Cu substitution on the
9
94

100
I

XRD patterns of smectites is unknown. It should be noted

Glycol

that the Cu smectite yakhontovite (CuO = 15.0–26.0 wt %)

Lump in rock , Rd

8.5
17.1

7.2

2 Crystallinity given as width at half-peak height divided by peak height for the (001) reflection
dÅ
Dull olive-green

has a 7.3 Å (12.1° 2θ) peak without being classified as a

mixed-layer phase (Postnikova et al., 1986; Jambor and
28
41

7.2 100
4.47 47
3.57 73
3.10 13
2.56 24
1.485 32
I
1.1 ± 0.2

Puziewicz, 1991; International Centre for Diffraction Data,

Notes: Only significant peaks are listed; dry runs: 3° to 65°, glycolated runs: 3° to 16°
Dry

1 The 7Å/14Å, i e., the ratio between the intensities of the (002) and (001) reflections

1993).
2.42
0.09

dÅ

15.2
13.0
RT-2915-B

16.8 100

8
13
I

Copper in the crystal structure

Glycol
Patches in rock, Rp

The main evidence indicating that copper is structurally

8.5
7.2
dÅ
Pistachio green

bound in the smectites of Radomiro Tomic is (1) the positive

correlation between Cu and structurally dependent parame-
56
100

17
32
19
41
9
4
I
1.4± 0.4

Dry

ters, such as the d-spacing of the (060) reflection (Fig. 15); (2)
1.492
4.47
3.58
3.12
2.57
0.17
0.03

dÅ

the change from anomalous compositions to a normal trend if

15.2
12.7

7.2

3 Average Cu content and standard deviation (wt %)

Cu is treated as another cation in the plot against Al (Fig. 13);

100

and (3) the change from a poor to an almost perfect negative

I
Glycol
Feldspar pseudom., F
Pale yellow to white

correlation between Fe + Mg alone on the one hand, and Fe

17.4

8.6
dÅ

+ Mg with Cu added on the other, in plots against Al(VI) (Fig.

16). This correlation is valid for smectites with considerable
100
35

3
41

3.01 19
2.57 15
1.495 10

to high contents of Cu, as can be seen in a related plot of Cu

I
1.5 ± 0.1

Dry

against the cations that normally occupy octahedral positions

4.47
DDH-3758; 151.9 m

0.03
0.02

15.0
12.8

7.3
dÅ

in smectites (Al(VI), Fe, and Mg; Fig. 17A–C). Observations

(2) and (3) suggest that Cu occupies octahedral sites in the
17.1 100

11
I
Glycol

structure, which is consistent with experimental work on tran-

sition metals in smectites and chlorites (Mosser et al., 1990,
8.3
dÅ

1992; Bailey, 1991; Güven, 1991; Decarreau et al., 1992). At

Veinlet, Vg2

low concentrations of Cu (<0.5 atoms per formula unit based

100

8
86

3.01 28
2.57 36
1.498 18
5.5 ± 2.83

on 22 oxygens) the correlation between Cu and (Al(VI) + Fe

Dry
Green

4.47
0.081
0.022

14.7

7.3

+ Mg) breaks down, suggesting that Cu in this case is extra

dÅ

0361-0128/98/000/000-00 $6.00 414

 RADOMIRO TOMIC MINE, CHILE: Cu-INSOLUBLE MINERAL OCCURRENCES 415

FIG. 14. Representative X-ray diffractograms of smectites from Radomiro Tomic. The upper eight patterns illustrate air-
dried preparations and the two patterns at bottom, raised 50 counts, exemplify the changes after ethylene glycol solvation
(cf. Table 4).

0361-0128/98/000/000-00 $6.00 415

416 BRIMHALL ET AL.
FIG. 15. Plot of wt percent Cu vs. d-spacing of the (060) reflection for
smectites in veinlets (Cu-rich population) and rock sites (Cu-poor popula-
tion) in samples from Radomiro Tomic.
FIG. 16. Plots of Fe + Mg (A, C, and E) and Fe + Mg + Cu (B, D, and F)
vs. Al(VI) for smectites from Radomiro Tomic (at. proportions based on 22
oxygens; Al(VI) = Al in octahedral position). See Figure 11 for smectite
abbreviations.
0361-0128/98/000/000-00 $6.00 416
FIG. 17. Plots of atoms per formula unit Cu vs. Al(VI) + Fe + Mg for
smectites from Radomiro Tomic (at. proportions based on 22 oxygens; Al(VI)
= Al in octahedral position). A-C illustrate the trend for analyses with con-
siderable to high Cu contents, whereas D-F show the lack of correlation for
smectites with less Cu. See Figure 11 for smectite abbreviations.
structural (Fig. 17D–F). These smectites have Σ(VI) values
up to ca. 0.5 atoms per formula unit above the theoretical
value of 4 for dioctahedral smectites.
Conclusions
This study demonstrates that the acid-insoluble fraction of
atacamite zone copper at Radomiro Tomic, as about 30 per-
cent of the total Cu in feldspar-stable portions of the ore
where clays are uncommon, cannot be attributed to the pres-
ence of copper sulfides as was earlier suspected but rather is
due to microinclusions of atacamite with diameters on the order
of 1 to 8 µm contained in rock-forming feldspars and other
silicate minerals. The soluble copper fraction that is over 70
 RADOMIRO TOMIC MINE, CHILE: Cu-INSOLUBLE MINERAL OCCURRENCES
wt percent of the total Cu occurs generally as atacamite in
cracks, which upon crushing is exposed along surfaces of the
rock fragments. The disseminated microinclusions of ata-
camite are rarely exposed by crushing and remain inside of
their host silicate minerals.
In contrast, in copper clay ores, in zones with weak,
feldspar-destructive argillic alteration caused by supergene
solutions, the occluded copper is structurally bound in octa-
hedral sites of well-crystallized smectitic clays. The two dif-
ferent acid-insoluble components are products of contrasting
microchemical environments in a reactive potassium silicate
alteration gangue. In both cases, the hydrothermal alteration
was sufficiently weak to leave intact rock-mineral buffers ca-
pable of neutralizing acid and reducing fluids. This process
controlled the precipitation of copper on all scales—the
macrofield zonal scale (Cuadra and Rojas, 2001), the mi-
croscale of individual crystals in cracks, and the atomic scale
of octahedral sites in the clay structure. It is very unlikely
that the considerable to high copper contents of many
smectites analyzed here are the consequence of included
particles and microveinlets of atacamite. The general lack of
correlation between Cu and Cl (Fig. 18A-B) for samples
with greater than 3 percent Cu argues against it. However,
for samples with less than 3 percent Cu, the weak correlation
of Cu and Cl suggests a possible exisitence of atacamite
FIG. 18. Plots of Cl vs. Cu of clays (A-C; the arrow indicates the trend if
included atacamite would be responsible for the Cu content of the smectites;
the vertical population in A is shown expanded in B) and CuO vs. SiO2 (D;
the arrow gives corresponding trend for chrysocolla). See Figure 11 for smec-
tite abbreviations.
0361-0128/98/000/000-00 $6.00 417
417
microinclusions. The most Cu rich smectites, in samples
DDH-3758 and RT-13014, are Cl free (Cl values less than
0.1 wt % are not significant; Table 3). Chlorine-bearing
smectites with Zn instead of Cu in hydrothermally altered
dacitic rocks were reported by Pons et al. (1989; Zn was not
detected in the Radomiro Tomic clays). It is also unlikely that
the considerable to high Cu contents are due to included
chrysocolla because this would not explain the weak negative
correlation between CuO and SiO2 (Fig. 18D). Microinclu-
sions of atacamite might, nevertheless, account for part of
the Cu in smectites with relatively low Cu contents forming
pseudomorphs after feldspar (Figs. 17D-F, 18C), as shown
by the lack of correlation between Cu and the sum of Al(VI),
Fe, and Mg.
The Radomiro Tomic smectites resemble copper-bearing
clay minerals described from two other deposits (Table 5)—a
megascopically similar sample from the oxidation zone of the
Potrerillos copper porphyry, 460 km south of Radomiro
Tomic (CC-1; Levi, 1997) and the Cu smectite yakhontovite
reported from an oxidized Cu-Sn deposit in Russia (Post-
nikova et al., 1986; see summary in Jambor and Puziewicz,
1991). The smectites of the three deposits have yellowish-
green colors in common and copper seemingly occupies octa-
hedral sites (Fig. 19). A chemical comparison (Table 5, Fig.
19) indicates that structurally bound Cu can occur in differ-
ent species: (1) di- to trioctahedral smectites at Radomiro
Tomic—low Cu grains have a typical dioctahedral chemistry
and (060) reflection (montmorillonites), whereas Cu-rich
grains show a trend toward a trioctahedral, saponitic chem-
istry; (2) saponites and mixed-layer smectite-chlorite phases
at Potrerillos with values of ca. 1.53 Å for the (060) reflection;
(3) the Cu smectite yakhontovite, which is classified as dioc-
tahedral in the International Centre for Diffraction Data
(1993) but described as dioctahedral with a certain trioctahe-
dral character by Postnikova et al. (1986); the dioctahedral
value for the (060) reflection (1.518 Å) is contradicted by a
trioctahedral chemistry (Fig. 19C).
Yellowish-green copper-bearing clay minerals have been
found in the oxidation zone of several porphyry copper de-
posits in northern Chile (E. Tidy, unpub. information). In ad-
dition, smectites with structurally bound transition metals
such as Ni, Co, Zn, Cu, and Mn are known to occur in the su-
pergene part of some ore deposits (Paquet et al., 1987; Güven,
1991) and in the vicinity of smelters (Rybicka and Jedrze-
jczyk, 1995; see Cuadra and Rojas, 2001, for one viewpoint).
The microinclusions of atacamite in rock-forming minerals
and copper-bearing smectites documented in this study owe
their existence to the relatively small amount of feldspar-de-
structive hydrothermal alteration that has affected Radomiro
Tomic. In contrast, many other South American porphyry
copper deposits have experienced strong, late-stage hydro-
lytic (sericitic) alteration and, hence, offer less reactivity to
applied acid solutions. The conditions of formation of the oc-
cluded copper phases is thought to be low-temperature su-
pergene, not high-temperature hypogene. However, the ori-
gin of the causative fluid, its salinity, age, and direction of
movement are presently under investigation.
The metallurgical implications of the copper-bearing mi-
croinclusions are that to expose them on fragment surfaces
would require fine grinding to a grain size well below 400
418 BRIMHALL ET AL.

TABLE 5. Chemical Analyses of Cu-Bearing Smectitic Clay Minerals from the Oxidation Zone of Three Deposits

Rodomiro Tomic1 Potrerillos2 Komsomolsk region3

Deposit Chile Chile Russia

Sample RT-13014 DDH-3758 All CC–1 Yakhontovite

Analysis Vg, 9 Vg2, 29 Mean SD a1 (14) a2 (9) b1 (8) b2 (1) 1 2 3

SiO2 43.66 51.04 53.49 2.37 47.80 48.91 36.65 35.71 48.83 48.62 53.94
Al2O3 9.55 14.75 21.76 4.84 3.41 0.49 16.00 12.69 0.30 0.42 0.08
FeO 3.03 4.68 5.77 2.42 28.81 33.62 11.84 16.66 6.51 9.96 10.34
MgO 0.61 0.80 1.25 0.59 1.11 0.73 21.07 18.63 10.15 1.39 6.11
CaO 0.98 0.94 1.07 0.34 2.81 2.85 0.70 1.15 3.46 1.56 2.58
Na2O 1.23 0.81 0.83 0.71 0.00 0.00 0.17 0.13 0.05 – –
K2O 0.19 0.72 0.34 0.29 0.29 0.13 0.08 0.14 0.12 0.06 –
CuO 28.75 14.27 3.50 3.91 3.77 1.27 1.49 2.89 18.59 25.99 14.95
Sum 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00 88.00
Cu 22.97 11.40 2.79 3.12 3.01 1.01 1.19 2.31 14.85 20.76 11.94

At. proportion based on 22 oxygens

Si 7.29 7.68 7.50 0.31 7.88 8.15 5.56 5.64 7.86 8.24 8.49
Al(IV) 0.71 0.32 0.50 0.31 0.12 2.44 2.36 0.06 0.00 0.00
Σ(IV) 8.00 8.00 8.00 8.00 8.15 8.00 8.00 7.92 8.24 8.49

Al(VI) 1.17 2.29 3.08 0.47 0.54 0.10 0.42 0.01 0.00 0.08 0.01
Fe 0.42 0.59 0.68 0.30 3.97 4.69 1.50 2.20 0.88 1.41 1.36
Mg 0.15 0.18 0.26 0.12 0.27 0.18 4.76 4.39 2.44 0.35 1.43
Cu 3.63 1.62 0.38 0.46 0.47 0.16 0.17 0.35 2.26 3.33 1.78
Σ(VI) 5.37 4.69 4.41 0.21 5.26 5.13 6.86 6.94 5.57 5.18 4.59

Ca 0.18 0.15 0.16 0.05 0.50 0.51 0.11 0.19 0.60 0.28 0.43
Na 0.40 0.23 0.22 0.19 0.00 0.00 0.05 0.04 0.02 0.00 0.00
K 0.04 0.14 0.06 0.05 0.06 0.03 0.02 0.03 0.02 0.01 0.00

At. proportion based on 28 oxygens

Si 9.28 9.77 9.55 0.40 10.03 10.38 7.08 7.18 10.01 10.49 10.80
Al 2.39 3.33 4.56 0.91 0.84 0.12 3.64 3.01 0.07 0.11 0.02
Fe 0.54 0.75 0.87 0.38 5.06 5.96 1.91 2.80 1.12 1.80 1.73
Mg 0.19 0.23 0.33 0.15 0.35 0.23 6.06 5.59 3.10 0.45 1.82
Cu 4.62 2.06 0.49 0.59 0.60 0.20 0.22 0.44 2.88 4.24 2.26
Ca 0.22 0.19 0.20 0.07 0.63 0.65 0.14 0.25 0.76 0.36 0.55
Na 0.51 0.30 0.28 0.24 0.00 0.00 0.06 0.05 0.02 0.00 0.00
K 0.05 0.18 0.08 0.06 0.08 0.04 0.02 0.04 0.03 0.02 0.00

Σ interlayer 0.78 0.67 0.57 0.44 0.71 0.68 0.23 0.33 0.81 0.38 0.55
Σ noninterlayer 17.02 16.14 15.79 0.27 16.88 16.90 18.91 19.02 17.17 17.08 16.64

1 Thisstudy; Vg and Vg2 are green veinlets (see Table 3); all = average with standard deviation for the 142 smectite analyses
2A Cu porphyry deposit 460 km south of Radomiro Tomic; a1 = smectite, a2 = Fe-rich smectite, b1 = mixed–layer smectite-chlorite, and b2 = Fe-rich
mixed-layer smectite-chlorite (number of averaged analyses in parentheses); energy dispersive spectroscopy data; Levi (1997)
3 A Cu-Sn deposit containing yakhontovite, a Cu smectite; electron microprobe data from Postnikova et al. (1986)

mesh. Secondly, besides the inordinate cost of such fine
grinding, chemical extraction of microinclusion copper from
feldspar host phases would entail extremely high acid con-
sumption, since increased hydrolysis of feldspars by chemical
reaction with acid would result and cause neutralization.
In the case of Cu smectites, since the copper occurs in
structurally bound, nonexchangeable, noninterlayer, octahe-
dral sites, any process envisioned to remove the copper would
necessarily have to avoid ion exchange as a recovery mecha-
nism. Alternatives to ion exchange could involve destabilizing
the smectite host, perhaps by its conversion to kaolinite which
may only incorporate copper or other divalent cations in neg-
ligible amounts.
The relevancy of process mineralogy guided by a geologic
appreciation of ore genesis mechanisms has never before
been as important as it is today, because heap leaching tech-
nology is begining to supercede pyrometallurgical smelting as
the extraction method of choice worldwide. Atmospheric
emissions are acquiring unprecedented environmental con-
sideration and what acid is recovered from stacks is recycled
and used in leaching.
Acknowledgements
This paper is dedicated in memory of our former professors
who taught a group of classmates petrology at the University

0361-0128/98/000/000-00 $6.00 418

 RADOMIRO TOMIC MINE, CHILE: Cu-INSOLUBLE MINERAL OCCURRENCES 419

FIG. 19. Comparison of Cu-bearing smectitic clay minerals in samples from the oxidation zones of Radomiro Tomic (RT,
all analyses of this study) and two other deposits: the Potrerillos Cu porphyry (CC-1 Smt = smectite, CC-1 mix-l. = mixed-
layer smectite-chlorite; Levi, 1997) and a Russian Cu-Sn deposit (Yakh. = yakhontovite, a Cu smectite; Postnikova et al.,
1986). The legend of the diagrams is given in D (see Figs. 12-13 for the chlorite and smectite fields).

of California, Berkeley. Charles Meyer and Frank Turner
were rare teachers whose skills with the microscope and ded-
ication to education serve as an inspiration to us to solve prac-
tical problems in industry. Through our professional careers
we have been guided by Chuck’s encouragement: “If all else
fails, just look at it.”
We are grateful for very helpful reviews by Eugene Ilton, A.
Decarreau, and John Dilles. The composite samples were se-
lected by Gonzalo Rojas and checked by Patricio Cuadra for
suitability. John Donovan assisted in the electron microprobe
work.
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