American Mineralogist, Volume 89, pages 13591366, 2004

Invisible gold revealed: Direct imaging of gold nanoparticles in a Carlin-type deposit

CHRISTOPHER S. PALENIK,1,* SATOSHI UTSUNOMIYA,1 MARTIN REICH, 1 STEPHEN E. KESLER, 1
LUMIN WANG, 1,2 AND RODNEY C. EWING1,2
1
Department of Geological Sciences, University of Michigan, Ann Arbor, Michigan 48109-1063, U.S.A.
2
Department of Nuclear Engineering and Radiological Sciences, Ann Arbor, Michigan 48109-2104, U.S.A.

ABSTRACT
Although As-rich, hydrothermal overgrowths on pyrite have been recognized as the primary host
phase for Au in Carlin-type deposits in Nevada, the chemical and structural state of the Au has remained
unresolved. Spectroscopic and electron imaging techniques have suggested that Au is either structur-
ally bound (e.g., Au1+) or occurs as particles of native Au (Au0), but the latter has never been observed
directly. We have determined that Au is present in signicant quantities as discrete nanoparticles of
native Au (~510 nm) in As-rich overgrowths on pyrite from the Screamer deposit in the Carlin trend,
Nevada, using analytical and high-resolution TEM and high-angle annular dark-eld (HAADF) imag-
ing in STEM mode. Electron microprobe and secondary ion mass spectrometry (SIMS) analyses of
the As-rich rims containing the Au-particles reveal that these rims (120 m) contain up to 0.8 wt%
Au, among the highest Au-contents ever reported for arsenian pyrite. These observations suggest two
possible mechanisms for nanoparticle formation: that Au exceeded its solubility limit in arsenian pyrite
causing it to be deposited as nanoparticles of native metal; or that exsolution of native metal from
metastable arsenian pyrite was caused by a later event in the history of the deposit.

INTRODUCTION
The Carlin-trend in Nevada hosts some of the worlds largest
Au deposits, reaching a maximum of about 40 million ounces in
the Betze-Post-Sreamer deposit (Leonardson and Rahn 1996; Ye
et al. 2003). Most of the Au is associated with very ne-grained
arsenian pyrite containing up to 1 wt% Au that forms rims on
earlier pyrite or solitary, porous aggregates (Fleet et al. 1997;
Simon et al. 1999a; Ye et al. 2003). These large concentrations
of Au have not been observed directly, an attribute that has led
to the term invisible Au being applied to ore in Carlin-type
deposits.
Numerous analytical methods have been used to study the
chemical state of invisible Au in arsenian pyrite and other
minerals, including electron microprobe analysis (EMPA) (Wells
and Mullens 1973), Mssbauer (Friedl et al. 1995; Genkin et
al. 1998), X-ray photoelectron spectroscopy (XPS) (Fleet et al.
1993; Maddox et al. 1998), X-ray absorption near-edge structure
(XANES) (Simon et al. 1999a, Cabri et al. 2000), and extended
X-ray absorption ne structure (EXAFS) spectroscopies (Simon
et al. 1999b). Combined, these indirect experimental observa-
tions suggest that Au is most likely present as either Au0 or Au1+,
although Au1 and Au3+ also have been suggested as the possible
state of Au. The phases and analytical techniques used to deter-
mine this range of Au speciation are summarized in Table 1 and
illustrate the degree of controversy that exists over the chemical
state of Au in As-rich, Fe sulde minerals.
The use of secondary ion mass spectroscopy (SIMS) imaging
also has been applied to the question of Au speciation (Bakken
* E-mail: cpalenik@umich.edu
et al. 1989; Cook and Chryssoulis 1990; Marion et al. 1991a,
1991b; Arehart 1993; Mumin et al. 1994; Fleming and Bekken
1995; Ye et al. 2003). SIMS images showing concentrated ar-
eas of Au have suggested the presence of native Au inclusions;
furthermore, SIMS depth-concentration proles suggest that Au
is distributed heterogeneously in the matrix (Pals et al. 2003).
However, the spatial resolution, limited by a 1020 m minimum
spot size, has prevented true resolution of individual particles or
any distinction from concentrated regions of chemically bound
Au (Cook and Chryssoulis 1990; Arehart et al. 1993; Marion et
al. 1991a, 1991b; Ye et al. 2003).
High-resolution transmission electron microscopy (HRTEM),
which provides resolution as good as ~2 , has been applied
in several studies in an attempt to conrm the presence of Au
nanoparticles (Yang et al. 1998). Despite the improved resolu-
tion, none of these studies identied Au in sufcient quantities to
account for the high concentrations of Au measured in the rims
of arsenian pyrite. Bakken et al. (1989), Hochella et al. (1998),
and Bakken et al. (1991) located a few isolated Au particles (<20
nm) in samples from Carlin Au-deposits associated with pyrite,
quartz, cinnabar, and illite. Other studies found arsenian pyrite to
consist of highly crystalline regions with no nanoparticulate Au
(Cabri et al. 1989; Fleet et al. 1989; Simon et al. 1999a). Cabri
et al. (1989) attributed stacking faults within the arsenian pyrite
matrix to arsenopyrite interlayers, a potential host for Au (Fleet
et al. 1989; Simon et al. 1999a). The size of these interlayers
(~10 wide) prevented a detailed study and conrmation of the
presence of Au.
Utilizing a high-grade Au sample, careful sample prepara-
tion techniques, and HRTEM combined with high-angle annular
dark-eld scanning transmission electron microscopy (HAADF-

0003-004X/04/00101359$05.00 1359
1360 PALENIK ET AL.: DIRECT IMAGING OF GOLD NANOPARTICLES

TABLE 1. Oxidation states of Au identied in arsenian pyrite and nanoparticulate Au by several indirect methods (Bakken et al. 1989; Mumin et al.
arsenopyrite, with method and reference 1994), we conclude that the nanoscale textures observed in this work were formed
Oxidation Phase Method Reference under natural conditions.
state
Au1 pyrite-arsenopyrite XPS Li et al. 1995 RESULTS
Au0 arsenopyrite XANES Cabri et al. 2000
arsenian pyrite XANES, EXAFS, SIMS Simon et al.1999a, b Gold nanoparticles
Au+1 arsenopyrite XANES Cabri et al. 2000 The Au content of the arsenian pyrite rims in SJ-323C-1326
arsenian pyrite XANES, EXAFS Simon et al.1999a
suldes Mossbauer Cardile et al. 1993 is among the highest reported from Carlin-type deposits (Reich
suldes XPS Jean and Bancroft 1985 et al. 2003; Ye et al. 2003). The average Au-content of the SJ-
arsenian pyrite XANES, EXAFS, SIMS Simon et al. 1999a, b
Au +3
arsenian pyrite Charge Balance Arehart et al. 1993
323C-1326 hand sample is 154 ppm Au (3.6 wt% As), and the
arsenopyrite Charge Balance Johan et al. 1989 120 m-thick overgrowths contain as much as 0.51 wt% Au
(10 wt% As) as determined by SIMS analyses and 0.8 wt% Au
STEM) (Utsunomiya et al. 2002; Utsunomiya and Ewing 2003), (8.1 wt% As) as determined by EMPA (Ye 2000). The higher Au
we have located regions containing large concentrations of Au content obtained using EMPA relative to that obtained by SIMS
nanoparticles in an arsenian pyrite overgrowth. Here we report analyses is likely a result of the smaller analytical volume of the
the identication and characterization of these Au-nanoparticles EMPA (~10 m3 for EMPA vs. 10001500 m3 for SIMS). Ad-
and the surrounding As-rich matrix and suggest two possible ditionally, EMPA data show that the Au content of the arsenian
mechanisms for the formation of nanoparticulate native Au: (1) pyrite rims in sample SJ-323C-1326 varies over a range of 0.36
that they were deposited directly from solution during precipi- to 0.84 wt% Au, as shown in Table 2. The EMPA data tabulated
tation of arsenian pyrite (i.e., that the solubility limit of Au in were collected from only the thickest of the As-rich rims to
arsenian pyrite was exceeded); or (2) that Au exsolved from ensure accurate analyses.
metastable arsenian pyrite after it was deposited (Palenik et al. Figure 1a shows a reected light photomicrograph of a typical
2002; Reich et al. 2003). As-rich overgrowth in sample SJ-323C-1326. After preparation
by tripod polishing, the sample was thinned to allow observation
SAMPLES AND METHODS
of the As-rich rim, as shown in the secondary electron (SE) image
The sample used in this study (SJ-323C-1326) was collected from the Screamer
in Figure 1b. In an attempt to locate Au, this region was investi-
zone of the Betze-Post-Screamer deposit in Carlin trend located in northeastern
Nevada (Leonardson and Rahn 1996; Ye et al. 2003). The sample consists of pyrite gated using HAADF-STEM, which provides an image contrast
(5.5%) in a quartz and kaolinite matrix. Back-scattered electron (BSE) imaging that is correlated positively with atomic mass (Utsunomiya and
was completed using a HITACHI S-3200N SEM. The chemical composition was
determined by electron microprobe analysis (EMPA) using a CAMECA SX100. An
accelerating voltage of 15 keV and beam current of 40 nA was used. The Cameca
PAP correction was used to reduce the data. Standards used were pyrite for Fe and
S, arsenopyrite for As, and native Au for Au. Four TEM samples were prepared
carefully from two thin sections of sample SJ-323C-1326 using a tripod polishing
method to create a thin edge that intersected the As-rich rims of the pyrite grains.
Final thinning was carried out using a 4.0 keV Ar ion beam in a GATAN precision
polishing system (< 30 minutes/sample). The TEM specimen holder was cleaned
with plasma (Fischione Model C1020) to minimize hydrocarbon contamination.
HRTEM was completed using a JEOL JEM2010F eld emission gun microscope
with an EDAX energy dispersive X-ray spectrometer (EDS). EDAX Genesis
software was used for point analysis and provided semi-quantitative elemental
characterization (~1 wt% detection limit). Nano-scale elemental mapping was
completed by HAADF-STEM coupled with Emispec ES Vision version 4.0.
To minimize the effect of sample drift, drift-correction mode was used during
the acquisition of EDS maps. STEM specications: Cs = 1.0 mm; probe size =
0.5 nm for analysis and 0.2 nm for high-resolution imaging; collection angle of
HAADF detector = 50110 mrad; objective aperture size = 30 m for analysis and
20 m for high resolution imaging; defocus condition 55 nm. Image process-
ing, including the fast Fourier transformation (FFT), was completed using Gatan
Digital Micrograph 3.4.
The possibility of sample alteration due to electron beam irradiation was noted
by Aylmore (1995), who observed the degradation of arsenopyrite (FeAsS) to pyr-
rhotite (Fe1xS) plus native Au under a focused electron beam. Alymore reported that
arsenian pyrite did not decompose under the electron beam. In our TEM examina-
tions, no changes in the sample morphology or structure were noted during the
course of examination. To test for sample alteration that may have been the result
of electron beam damage or ion milling, additional TEM samples were prepared
by polishing only (i.e., ion milling was omitted). The electron beam was focused
(current density = 510 pA/cm2) on the As-rich rim in both regions containing Au-
particles and those that did not contain Au. After 5.5 min, no change to the lattice
structure could be detected. The electron beam conditions used in this test were
far more extreme than those experienced by the samples during normal sample FIGURE 1. (a) Reected light image of Au-rich arsenian overgrowth
characterization. Utsunomiya et al. (2004) carried out a study of arsenopyrite in on pyrite. (b) Secondary electron image of the same area of the sample
pegmatite using similar sample preparation and examination conditions and found after tripod polishing and ion milling to create a thin edge in the gold-
no alteration to the sample. Based on the above precautions and the prediction of rich rim.
 PALENIK ET AL.: DIRECT IMAGING OF GOLD NANOPARTICLES 1361

Ewing 2003). In our samples, Au particles appear bright against of the surrounding matrix did not detect Au (detection limit ~1
the lower average atomic mass of the Fe-As sulde matrix. Ob- wt%). Based on a digital analysis of HAADF STEM images,
servation of the As-rich rims with this technique revealed a large such as the one shown in Figure 2, the nanoparticles occupy
concentration of relatively high-contrast particles with a subhe- approximately 1 ( 0.5) vol% of the matrix. Assuming an arse-
dral to anhedral morphology (~110 nm in the diameter) against a nian pyrite matrix with 10 wt% As, this Au-particle-rich region
darker (lower average atomic weight) matrix (Fig. 2). Nano-scale contains an estimated 4 wt% Au, which is 5 to 10 times higher
elemental maps showed that the particles are composed mainly than the Au content measured by EMPA (0.37 0.80 wt%).
of Au (Fig. 3). Indexing of the two-dimensional lattice fringes Furthermore, Au is distributed heterogeneously in the arsenian
in HRTEM images of these particles conrmed that the particles pyrite matrix at length scales shorter than those measurable by
have the crystal structure of elemental Au, as illustrated by the EMPA. This nding suggests that Au-poor zones must also be
HRTEM image of the [011] zone axis of Au (Fig. 4). present in the arsenian pyrite in order to yield the average Au
Qualitative analysis of the EDS spectrum from these particles contents measured by EMPA for the arsenian pyrite rims. TEM is
indicates an Au concentration of about 1.5 wt%. EDS analysis limited to relatively small areas of observation (i.e., the thinned
edge of the TEM sample), and thus, the regions observed are
TABLE 2. EMPA analyses of Au-bearing rims in the Screamer sample not necessarily representative of the entire sample. However,
SJ-323C-1326
both areas of arsenian pyrite with and without Au nanoparticles
Au (wt%)* As(wt%)
were observed in the sample. This analysis demonstrates the
0.587 6.928
0.697 8.463 signicance of choosing length-scale appropriate techniques
0.839 8.073 when studying nano-scale phases (McCrone 1968).
0.564 7.771
0.707 8.534
0.628 7.942
Arsenic-rich matrix
0.641 8.247 The As-rich matrix exhibits two nanostructure textures, de-
0.365 7.306
0.702 7.931 pending on whether or not native Au is present. In the presence
0.5133 (SIMS, Ye) 9.93 (SIMS, Ye) of Au nanoparticles, the matrix consists of a polycrystalline,
* Note that EMPA data presented in this table represent analyses on only the
thickest rims (>10 m) to ensure analysis accuracy.

FIGURE 4. (a) HRTEM image of a gold particle in a polycrystalline

FIGURE 2. HAADF STEM image of Au particles (light contrast
particles) dispersed throughout an As-rich iron sulde matrix.
matrix. An As-rich iron sulde domain partially surrounds the gold
particle. Note that the gold particle and the crystalline sulde domain
share a common lattice fringe despite the change in lattice dimension
noted on the gure. (b) In the fast Fourier transform image, the diffraction
maxima were indexed to be those of gold [011].

a b c

FIGURE 3. Elemental maps

of a gold particle: (a) AuL (b)
FeK, (c) SK
1362 PALENIK ET AL.: DIRECT IMAGING OF GOLD NANOPARTICLES
FIGURE 5. HRTEM image of the randomly oriented polycrystalline
domains surrounding the gold particles. Two of the polycrystalline
domains have been outlined (dotted line).
As-rich, Fe sulde (Fig. 5), whereas matrix regions barren of Au
particles consist of a highly crystalline arsenian pyrite (Fig. 6).
The As-rich matrix where Au particles are absent (Fig. 6) con-
sists of arsenian pyrite, as determined by selected-area electron
diffraction (SAED) and HRTEM lattice images (Bayliss 1977).
Using TEM, Fleet et al. (1993) observed a crystalline arsenian
pyrite matrix in which no Au (structural or native) could be
detected. Fleet et al. (1993) also observed 10 stacking faults
in the arsenian pyrite lattice; a feature attributed to possible arse-
nopyrite or marcasite interlayers. Although the interlayers were
too thin to be analyzed, they were suggested as a possible host
phase for Au. No such dislocations were observed in our samples.
Semi-quantitative EDS of the crystalline matrix in Figure 6 using
a focused electron beam (1 nm) detected ~5 wt% As, but no Au.
The lack of visible Au particles implies that any Au present in the
arsenian pyrite is structurally bound and present at <1 wt% levels
(detection limit of EDS). With a maximum Au-concentration of
up to only 0.84 wt% in the matrix, as determined by EMPA, the
higher detection limit of the HRTEM-EDS analyses would not
permit identication of structurally bound Au.
The As-rich matrix that contains Au-particles consists of a
polycrystalline aggregate of at least two phases (Fig. 5). Indi-
vidual domains are approximately 20 nm2 and oriented randomly.
Elemental maps of multiple domains show a heterogeneous dis-
tribution of As, commonly with elevated concentrations of As
adjacent to Au particles (Fig. 7). Because domains had a random
orientation and small size, most yielded, at best, a one-dimen-
sional lattice fringe. In an attempt to use an oriented zone axis
(i.e., a two-dimensional lattice fringe image) to characterize the
phase(s) present in the polycrystalline rim material, the sample
was tilted. Even with tilting, however, orientation of the matrix
phase proved to be difcult. Characterization of the lattice fringe
images also was limited by similarities in lattice spacing shared
by many of the Fe suldes as well as the ultimate accuracy in
measuring lattice spacings from HRTEM images. In particular, it
was difcult to distinguish conclusively the images of pyrrhotite
from those of arsenopyrite at the observed orientations.
Over 100 HRTEM images of polycrystalline matrix were
collected near Au particles in 30 different domains. Based on
FIGURE 6. HRTEM image of crystalline arsenic-rich matrix that
did not contain gold particles and inset indexed diffraction pattern of
the arsenian pyrite.
the domains that could be indexed from lattice fringes, the
matrix appears to be a mixture of two phases (in addition to
the Au-particles): (arsenian) pyrite and either arsenopyrite or
pyrrhotite. Figures 8a and 8b show indexed HRTEM images of
two representative domains near Au particles. Figure 8a shows
a domain indexed as (arsenian) pyrite, and Figure 8b shows a
domain indexed as either arsenopyrite or pyrrhotite. Interplanar
spacings for the indexed diffraction maxima of Figure 8b are
presented in Table 3, illustrating the similarity of the HRTEM
image of arsenopyrite to that of pyrrhotite. Based on analysis of
all structural data in the 30 domains, 2 domains were determined
to be consistent with (arsenian) pyrite, whereas 10 domains were
attributed to arsenopyrite (or pyrrhotite). The other 18 domains
could not be characterized structurally.
The possibility of two (or more) co-existing As-rich Fe sulde
phases is not without precedent. Mumin et al. (1994) discussed the
alteration of Fe sulde phases and identied coexisting arsenopyrite
and arsenian pyrite. Putnis (1975) described the TEM observation
of coexisting pyrrhotite phases. Further complicating the interpreta-
tion is the limited knowledge of the stability elds of As-rich Fe
suldes. For example, existing experimental work has not estab-
lished a stability eld for arsenian pyrite (Clark 1960; Morimoto
and Clark 1989; Wu and Delbove 1989; Wu et al. 1990).
Another characteristic of the polycrystalline matrix is the
alignment of lattice fringes between some Au particles and the
adjacent sulde domain. Figure 4 is highlighted (parallel white
lines) to illustrate the alignment between the fringes of the 2.3
spacing of the (111) diffraction maximum in Au with the 2.6
matrix lattice, which corresponds to either the (203) spacing
of pyrrhotite or the (020) spacing of arsenopyrite.
DISCUSSION
Gold nanoparticles
For some time, it has been acknowledged that the majority
of Au present in Carlin-type Au samples is associated with As-
 PALENIK ET AL.: DIRECT IMAGING OF GOLD NANOPARTICLES 1363

a b

c d

FIGURE 7. Elemental maps of the Au-rich matrix showing

a heterogeneous distribution of arsenic. (a) FeK, (b) SK, (c)
AsL, (d) AuK.

TABLE 3. Comparison illustrating the similarity of indexed diraction maxima in Figure 8b for arsenopyrite and pyrrhotite
Measured Arsenopyrite (PDF no. 14-218) Pyrrhotite-3t (PDF no. 24-220)*
Spacing Dist. (A) Angle Spacing Dist. (A) Angle Spacing Dist. (A) Angle
1 2.59(5) 62.6(4) 112 2.559 63.2 203 2.635 62.4
2 5.67(5) 010 5.675 003 5.687
* Pyrrhotite-3T was chosen as a representative hexagonal pyrrhotite. Based on the sized of the domains
imaged, the various pyrrhotite polymorphs could not be distinguished structurally by TEM.
where number in parenthesis is the estimated error on the last decimal of the measurement.

FIGURE 8. Indexed HRTEM

and FFT images of identied
matrix phases in the Au bearing,
As-rich sulde matrix. Although
not every domain could be
uniquely identied, conrmed
matrix domains included (a)
pyrite and (b) arsenopyrite or
pyrrhotite. In (b) the FFT image
is indexed for both arsenopyrite
(asp) and pyrrhotite (pyr).
Boxed area shows location of
the identied phase.

rich pyrite. In this work, Au nanoparticles (510 nm) have been
identied at concentrations of up to 4 wt% in some regions of
the arsenian pyrite rim, high enough to account for the majority
of Au present in the hand sample. The successful observation of
discrete Au nanoparticles was likely due in part to several fac-
tors: (1) the ore sample that we studied had a much higher Au
content than samples previously examined by TEM [154 ppm
in SJ-323C-1326 (this work) vs. 60 ppm (Bakken et al. 1989)];
(2) although sample preparation methods used in this work were
nominally similar to those used in other studies (i.e., polishing
followed by ion milling), the tripod polishing technique em-
ployed here allowed us locate the thin edge of our TEM sample
precisely within the As-rich rim (Fig. 1), effectively focusing
our examination toward a specic region of the sample; and (3)
the application of HAADF-STEM imaging to the study of heavy
metal nanoparticles allows for fast scanning of the matrix for
1364 PALENIK ET AL.: DIRECT IMAGING OF GOLD NANOPARTICLES
particles of interest (Utsunomiya and Ewing 2003).
Previous spectroscopic studies have reported the indirect ob-
servation of native Au, chemically bound Au, or both forms in
arsenian pyrite from Carlin-type deposits (Table 1). In TEM study
of samples with lower concentrations of Au (up to 4400 ppm Au
in arsenopyrite), Cabri (1989) did not locate Au in any form, but
did observe a long-range crystalline As-rich pyrite matrix. In our
study, in samples from an even richer ore (120 ppm Au, up to
0.84 wt% in arsenian pyrite rims), similar textures were observed
in areas free of Au particles. In Au-bearing areas, however, the
observed texture is considerably different and consists of a poly-
crystalline matrix with abundant Au-nanoparticles.
Mechanism of gold nanoparticle formation
We propose two possible origins for the Au nanoparticles:
(a) that the solubility limit of Au in arsenian pyrite (0.5 wt%
Au at 10 wt% As) was exceeded locally during crystallization
of the arsenian pyrite rims, resulting in deposition of elemental
Au; or (b) that the Au nanoparticles exsolved from a metastable
arsenian pyrite matrix during later stages in the evolution of
the deposit.
The rst mechanism for the formation of Au nanoparticles
requires that the solubility limit of Au in arsenian pyrite be ex-
ceeded during crystallization of the arsenian pyrite rims. This
mechanism implies that the arsenian pyrite structure can accom-
modate a limited amount of Au. EMPA analyses of As and Au
in arsenian pyrite suggest that the limit of structurally bound Au
accommodated by arsenian pyrite is dependent on, and increases
with, As content up to a limit of about 10 wt% As and 0.5 wt%
Au (Palenik et al. 2002; Reich et al. 2003). Thus, regions of the
arsenian pyrite rim that have exceeded the solubility limit of Au
in arsenian pyrite must contain native Au, apparently in the form
of nanoparticles, whereas the remainder of the matrix will retain
any Au within the arsenian pyrite matrix. The close spatial as-
sociation of regions with abundant Au particles to those without
Au particles may be attributed to variations in the Au content
of the hydrothermal solution though time, a common feature
of complex ore systems, or to precipitation of sub-microscopic
growth zones from different uids during the crystallization of
the arsenian pyrite rims.
The second mechanism for the formation of Au nanoparticles
involves exsolution of native Au particles from an Au-rich, meta-
stable arsenian pyrite matrix. Limited experimental and thermo-
dynamic studies of the Fe-As-S system that have been carried out
thus far provide no stability eld for arsenian pyrite, suggesting
that the arsenian pyrite observed in natural systems may exist as
a metastable phase. As noted above, available analyses of Au-
bearing arsenian pyrite indicate that maximum Au contents of
samples at room temperature increase directly with increasing As
contents (up to ~0.5 wt% Au at 10 wt% As). A similar solubility
limit probably prevails at higher temperatures typical of those
under which arsenian pyrite formed. If the solubility limits at
high and low temperature differ signicantly, exsolution might
be caused by decreasing temperature. In the case of a metastable
phase such as arsenian pyrite, even more subtle changes might be
enough to trigger the exsolution of Au in regions of the sample
with the highest Au content. Such an exsolution would advance
at the expense of the crystalline arsenian pyrite matrix, possibly
resulting in the formation of the randomly oriented polycrystal-
line As-rich and As-poor Fe sulde domains observed (Fig. 5).
In a sample such as SJ-323C-1326, which contains a wide range
of Au content (see Table 2), it is conceivable that on a micro-
scopic scale, areas with the highest Au content exsolved native
Au, whereas lower-grade regions of the sample retain structural
Au. This mechanism is supported by SIMS evidence (Mumin
et al. 1994), which suggested that Au evolved from primary
solid-solution within sulde/arsenide minerals to colloidal and
micrometer-size particles concentrated in voids, fractures, and
internal grain boundaries.
Regardless of the mechanism for Au-deposition, this sample
(SJ-323C-1326) presents a unique microenvironment in which
the variation in Au-content (0.474 wt% from Table 1) is greater
than the entire Au-content reported in any of the other 90 analyti-
cal points studied in samples by Ye (2000) from the Screamer
deposit. In such a sample, it is conceivable that small regions of
higher Au-content have exceeded the solubility limit of Au or
exsolved Au from arsenian pyrite, resulting in the formation of
Au-nanoparticles, whereas other regions of the sample with lower
Au-content might contain structurally incorporated Au (without
particles of native Au). This cannot be conrmed explicitly since
the presence of structurally incorporated Au in this sample cannot
be detected by EDS because the maximum Au content measured
by EMPA (0.838 wt%) is below the 1 wt% detection limit of EDS.
However, within the arsenian pyrite rims, both Au-particle-rich
regions and regions barren of Au particles have been located.
The scale at which exsolution reactions occur is also likely
to be a driving force toward the formation of native Au. At the
nanoscale, physical and electronic properties of materials differ
dramatically from those for bulk samples (Halperin 1986). For
example, at particle sizes of 20 nm and below, the melting point
of Au decreases dramatically from 1064 C (bulk), to 925 C
(10 nm) to 800 C (5 nm) to 500 C (2.5 nm) (Buffat and Borel
1976). Although the sample in this study did not experience
these high temperatures, this example serves to demonstrate the
dramatic property changes that can occur as particle and domain
sizes decrease, and surface area and surface energy increases.
Applied to this system, the electronic and physical properties at
the nanoscale appear to encourage exsolution (or precipitation)
of native Au. This method has already been demonstrated in
experiments involving recovery of Au from ores. Hoare et al.
(1999) described the thermal decomposition of pyrite into pyr-
rhotite in terms of kinetic parameters that were highly dependent
upon particle mass. Aylmore and Lincoln (1996) showed that the
application of energy to pyrite through mechanical milling can
cause exsolution of native Au.
It is possible that both of the mechanisms presented above
operated in a single sample at different times. Thus, consistent
with previous spectroscopic results, invisible Au is not neces-
sarily present in a single form, even within a single sample or
single As-rich rim.
Environmental and process availability of Au
Regardless of the formation process of nanoparticulate Au, the
resultant polycrystalline matrix in regions of nanoparticulate Au
increases the availability of Au from environmental and process
standpoints. Exposure to weathering or bio-oxidation (Canales
 PALENIK ET AL.: DIRECT IMAGING OF GOLD NANOPARTICLES
2002) will preferentially degrade the less robust polycrystalline
matrix containing the Au particles. Once liberated, the gold
nanoparticles will be dispersed throughout surrounding rocks
by colloidal transport (Traexler and Ewing 2002; Traexler et
al. 2004). The isolated Au particles adsorbed onto the surfaces
of cinnabar, quartz, and illite observed by Bakken et al. (1989)
probably resulted from this process, as perhaps did some of
the redistributed gold particles noted by Mumin et al. (1994).
Similar reasoning should apply to processes used to liberate Au
from arsenian pyrite, which commonly requires heating to be
converted to Fe oxides and hydroxides (Hausen 1981). Areas
of arsenian pyrite containing Au nanoparticles are probably the
least stable, suggesting that nanoparticle Au will be among the
earliest liberated forms of Au in this process. Finally, this process
may also be applicable to the concentration and recovery of Au
in mining operations.
ACKNOWLEGMENTS
C. Palenik would like to thank Z. Ye for supplying the sample for study and
K. Traexler and F. Skomurski for their helpful discussion on colloids. The authors
would also like to acknowledge C. Henderson, J. Manseld, and C. Wauchope for
their assistance with the electron microbeam techniques, and B. Bekken, M. Fleet,
and an anonymous reviewer for positive and helpful comments. Early support for
this research came from Barrick Gold Corporation through the good ofces of
Keith Bettles, and later phases were funded by a National Science Foundation grant
(NSF EAR 0207273) to S.E.K. and R.C.E. This research also was supported in
part by an Ofce of Civilian Radioactive Waste Management Fellowship (Palenik).
The results of this work were obtained at the University of Michigan Electron
Microbeam Analysis Laboratory and the equipment was obtained with support
from NSF grants EAR96-28196 and EAR99-11352.
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