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Crystalline Placer Gold from the Rio Neuquen, Argentina: Implications for the
Gold Budget in Placer Gold Formation

Article in Economic Geology · May 2003

DOI: 10.2113/98.3.623

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Economic Geology
Vol. 98, 2003, pp. 623–633

Crystalline Placer Gold from the Rio Neuquén, Argentina:

Implications for the Gold Budget in Placer Gold Formation
A. J. MCCREADY,†
Mineralogy & Petrology Group, Institute of Geological Sciences, University of Leoben, Leoben, Austria A-8700

J. PARNELL,
Department of Geology and Petroleum Geology, University of Aberdeen, Meston Building, King’s College,
Aberdeen, AB24 3UA, United Kingdom

AND L. CASTRO
Departmento de Ciencias Geológias, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires,
Ciudad Universitaria, Pab2, 1428, Buenos Aires, Argentina

Abstract
Recent fluvial sediments of the Rio Neuquén, Argentina, contain variable amounts of placer gold. In addi-
tion to rounded, detrital placer gold, the sediments also contain pristine crystalline gold (type 1 gold), which
occurs as overgrowths on detrital placer gold cores. Type 1 gold is locally rimmed by gold with a wormlike or
crystalline texture (type 2 gold). The chemistry of the primary cores indicates variable intragrain and intergrain
compositional heterogeneity. This is interpreted to indicate a multisource origin. Type 1 gold is composed of
virtually pure gold (>98 at. % Au) and type 2 gold is an Au-Hg amalgam (4–9 at. % Hg). Both varieties are au-
thigenic in origin.
The formation of the virtually pure type 1 gold is interpreted to be due to the addition of Au from an exter-
nal source, rather than by the removal of Ag and other metals. The AuHgAg type 2 gold is interpreted to be
due to Hg contamination from historic mining. Type 1 gold is interpreted to be analogous to the Ag-poor rims
present on many placer gold grains. The evidence presented in this study supports the view that the Ag-poor
rims on placer gold grains are the result of Au addition and not Ag removal. This study also has implications
for both quantitative morphological and paragenetic studies of placer gold grains.

Introduction 1988). However, the genesis and development of these rims

PLACER GOLD forms essentially as the result of weathering,
the mechanical liberation and the chemical dissolution of a
preexisting deposit. The gold is then redistributed and con-
centrated by mainly alluvial, eluvial, and chemical processes.
During transport in the mainly fluvial environment, originally
crystalline gold is deformed, abraded, and comminuted on
the streambed by saltation. The pronounced malleability of
particulate placer gold leads to the overall rounding or re-
shaping and peening of the gold grains during transport (Fig.
1A), and the acquisition of characteristic morphological fea-
tures, which include upturned rims and/or lips, accidentally
trapped mineral grains, and impact marks and tools marks
(Naden, 1988; McCready, 1999).
When a placer gold specimen is sectioned and examined, it is
typically observed to comprise an Au-Ag core surrounded by a
rim of gold that is Ag poor in composition (Fig. 1B; Desbor-
ough, 1970; Boyle, 1979; Giusti, 1986; Groen et al., 1990;
Knight et al., 1999a, b). The rims vary in size, reaching up to ca.
60 µm in width (Bowles, 1988; Groen et al., 1990), and may not
be of constant thickness around the grain margin (Naden,
1988). The rim always displays a sharp interface with the core of
the grain; no evidence of a gradational transition exists (Bowles,
1988; Naden, 1988; McCready, 1999). The Ag-poor rims are not
considered a primary feature; instead, they develop after the
grains have been liberated from their source rock (Bowles,
† Corresponding author: e-mail, mccready@unileoben.ac.at
have been the subjects of an ongoing debate over the past 30
years. Two schools of thought exist regarding their genesis: (1)
the rims are the result of Ag removal (e.g., Desborough, 1970;
Giusti and Smith, 1984; Michailidis, 1989; DiLabio, 1990;
Knight and McTaggart, 1990; Hérail et al., 1990; Krupp and
Wesier, 1992; Knight et al., 1999a, b); and (2) the rims are the
result of Au addition (e.g., Bowdish, 1983; Mann, 1984; Stoffre-
gen, 1986; Bowles, 1988; Groen et al., 1990; Bowell, 1992;
Craw, 1992; Santosh et al., 1992; Southam, 1998). However,
some workers (e.g., Loen, 1994; Youngson and Craw, 1995) sug-
gest that rim formation proceeds by both mechanisms.
In contrast to the typical placer forms, the work reported
here records the morphology, chemistry, and genesis of pris-
tine crystalline placer gold grains from the Rio Neuquén in
Argentina. Its crystalline morphology and chemistry pose
challenging questions. The occurrence of these pristine
placer gold grains has implications regarding several aspects
of placer studies, not least the origin of Ag-poor rims.
Location and Regional Geology
The Rio Neuquén is situated in the Neuquén province in
western Argentina within the Cordillera Principal of the cen-
tral Andes, close to the border with Chile (Figs. 2 and 3). The
study area straddles the boundary of the present-day and
Mesozoic magmatic arcs, and the metalliferous and petro-
leum-bearing Neuquén sedimentary basin, which forms part
of the system of sub-Andean foreland basins.

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624 MCCREADY ET AL.

o o
A 71 70

o
37 37o

Andacollo

Chos Malal

B Rio Neuquen
37.5o 37.5o

o o
38 38
o o
71 0 20 40 60 70

km
200µm
Sedimentary Igneous
FIG. 1. A. Secondary electron micrograph of a reshaped and deformed,
flakelike placer grain from Drumbolge, Donegal, Ireland. B. Back-scattered Intrusive Extrusive
electron micrograph of a placer gold grain from Kildonan, Scotland, showing Quaternary
the occurrence of a primary grain core (dark gray) surrounded by an Ag-poor
rim (light gray; from McCready, 1999). Tertiary

Cretaceous-Tertiary

Two extensive geotectonic units are recognized in the Jurassic-Cretaceous

study area, the first representing the Cambrian-Triassic in-
Jurassic
terval, the Gondwana cycle, and the second representing the
Jurassic-Quaternary interval, the Andean cycle (Fig. 3). Triassic
Remnants of the Gondwana cycle are exposed in the cores of
large anticlinal structures of the younger orogen; e.g., the Permian
Cordillera del Viento, where Carboniferous-Permian sand-
Carboniferous
stones and tuffs of the Andacollo Group are intruded by
FIG. 3. Generalized geology of the Rio Neuquén region (modified from
Mendez and Zappettini, 1989); heavy black rectangle indicates area of inter-
est. Bold line is Rio Neuquén.

Chile
36oS
granites and granodiorites of the Choiyoi Group, respectively
Argentina (Mendez and Zappettini, 1989).
Concepcion Chos The Andean cycle is marked by the development of the
Malal large petroleum-bearing Neuquén sedimentary basin from
the Jurassic until the Cretaceous. Deposition ceased during
STUDY AREA the late Cretaceous, due to basin tilting and uplift. Post-uplift,
widespread deposition of nonmarine red beds occurred dur-
38oS ing the late Cretaceous-Tertiary. However, only fragments of
0 km 100
Neuquen
these are still preserved (Mendez and Zappettini, 1989).
72oW 69oW Magmatic activity during the Cenozoic resulted in (1) the
FIG. 2. Location of the study area, showing the main hydrological systems. emplacement of magmatic bodies in the area, e.g., the Cerro
Chile-Argentina border depicted by dashed line. Mayal andesitic complex, and (2) the extrusion of flood basalt

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 CRYSTALLINE PLACER GOLD, RIO NEUQUÉN, ARGENTINA 625

over a broad area in the Neuquén basin. During the Pleis-
tocene and Holocene, the area was subjected to glacial, flu-
vial, and aeolian processes.
Primary Gold Deposits in the Area
The study area contains a number of gold mining districts,
including the Andacollo-Huinganco and La Primavera. Four
types of primary gold deposits are present in the area: (1) au-
riferous quartz veins (e.g., Rosario deposit); (2) galena-spha-
lerite-auriferous pyrite veins (e.g., Sofia deposit); (3) aurifer-
ous pyrite veins (e.g., Erika deposit); and (4)
disseminated-type gold deposits (e.g., Los Maitenes). The
gold deposits are related to the formation of the magmatic arc
during the Mesozoic orogen (Mendez and Zappettini, 1989).
Fluvial System
The Rio Neuquén basin has a catchment area of ca. 32,450
km2, with most of the water derived from the 270-km-long
Cordillera del Viento. The river rises in the Cordillera de los
Andes from narrow, V-shaped valleys. It flows southward
along the Cordillera del Viento (Fig. 4). At the confluence
with the Reñileuvú tributary, the Rio Neuquén changes its
course and flows eastward, oblique to the regional structural
pattern of the area. It continues to flow eastward for ca. 50
km until La Herradura, where it changes course to southeast-
ward flowing and into a meandering regime. At Chos Malal,
the Rio Neuquén is joined by its principal tributary, the “Rio
Curilieuvu” (Fig. 4).
The river has two torrential flow stages: one in winter
(June–September), owing to increased rainfall, and the other
in spring, owing to snow melt. In summer, the discharge falls
to around 306 m3/s.
Key
Huinganco Rio Neuquen
Tributary
nto
Methodology
River alluvium samples were collected along a 120-km sec-
tion of the Rio Neuquén, between Huinganco and Balsa
Huitrin, during three successive field seasons. A total of 320
samples were taken, with a sample interval of between 400
and 500 m. From the river alluvium samples, placer gold
grains were obtained by panning.
Gold grain morphology was determined on a JEOL WIN-
SEM 6400 scanning electron microscope (SEM), which is
equipped with both secondary and back-scattered electron
detectors. Gold grain chemistry was determined on a Jeol 733
electron microprobe using wavelength dispersion. Operating
conditions were 20-Kv accelerating voltage, 100-nA beam
current, and 2-µm beam diameter. Element concentrations
were calculated using SPECTA software. Metal standards
were used for Au, Ag, and Cu, and a mercury telluride (60.82
Hg, 39.18 Te) for Hg. Statistical analysis of the data was per-
formed; all data that were less than 2σ of the background
noise were considered to be below the detection limit. Com-
positions are quoted as at. percent, rather than wt percent or
fineness.
Crystalline Grain Morphology
In addition to rutile, monazite, pyroxene (augite and hy-
persthene), amphibole (hornblende), actinolite, olivine, zir-
con, apatite, magnetite, and barite (Castro and Gamba, 1994;
McCready, 1999), the heavy mineral assemblage of the Rio
Neuquén contains variable amounts of placer gold. In addi-
tion to the presence of typical rounded placer gold grains
(Fig. 5), the majority of the gold grains (ca. 65%) display pris-
tine crystalline morphologies referred to as type 1 (Fig.
6A–C). The crystals may be either hexagonal, cubic, octahe-
dral, or dodecahedral in nature. The individual crystals vary in
size from less than 10 to ca. 50 µm. The crystals often display
evidence of limited mechanical deformation in the form of
microtool marks (e.g., grooves, scours, pits, and abraded cor-
ners; Fig. 6D).
Many of the individual gold crystals possess enigmatic mi-
crocracks (Fig. 6B, D). These microcracks vary in length (up
to 20 µm), complexity (simple or bifurcated), and shape (e.g.,

Primary gold source

l V ie

straight or crescentlike). In all cases, they are open and not

Erica Mine
e

Sofia Primary barite source

C. D

Mine
Andacollo City

La
Herradura
La Primavera
Mayal
Chos Malal
A. R.

0 km 20
Balsa
Huitrin

FIG. 4. Diagram of the Rio Neuquén hydrological system, showing the oc-
currence of primary gold occurrences. A.R. = Reñileuvú Tributary, C. Del FIG. 5. Secondary electron micrograph of a rounded detrital placer gold
Viento = Cordillera del Viento. grain from the Rio Neuquén.

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626 MCCREADY ET AL.

A B

C D

FIG. 6. Secondary electron images of crystalline gold. A–C. General view of crystalline gold. D. Close up view of crys-
talline gold. Note the occurrence of microcracks in many crystals.

filled by other minerals. Each crack terminates in an arrow-
head-shaped, pointed tip.
In the majority of cases, the type 1 crystalline gold appears
to encrust a grain core, forming a rimlike structure. In most
cases, the grain core is visible either beneath the crystalline
gold or on another part of the grain (Fig. 6A, B). However,
the grain core is not always possible to recognize under SEM;
individual crystals may completely engulf the parental grain.
In these cases, the grain core is only visible upon sectioning
(Fig. 7A). In all cases, the contact between the grain core and
the crystalline gold is sharp. However, some of the gold has a
rounded protrusion or rounded wormlike morphology re-
ferred to as type 2. This gold mantles the compact crystalline
gold (Fig. 7B). No evidence of spongy and/or porous gold
(Naden, 1988; Krupp and Weiser, 1992) was observed.
The grain cores locally contain inclusions of euhedral
quartz. No such inclusions were noted in the crystalline gold.
When viewed under reflected light, after carbon coating,
the crystalline gold (type 1) appears as a vivid blue color,
whereas the finer-grained wormlike gold (type 2) appears as a
dark red color (Table 1).
Chemistry
Grain cores
The grain cores are composed of Au and Ag ± Hg. The Au
content of the grains ranges from 32.05 to 87.40 at. percent
Au. Silver contents range from 12.60 to 67.40 at. percent Ag.
Mercury is not present in all of the analyses; where present, it
reaches a maximum 1.49 at. percent Hg. Copper was de-
tected in only one analysis (0.13 at. % Cu); therefore, it is con-
sidered insignificant, with respect to the overall composition.
Multiple analyses of each grain indicate intragrain varia-
tion, with respect to the Ag/Au ratio (Fig. 8). The extent of in-
tragrain variation is not constant, but varies from grain to
grain; some grains vary by less than 5 at. percent Au, whereas
others vary by ca. 15 at. percent Au. Comparison of the aver-
age Au/Ag ratio of different grains (Fig. 8) indicates three dis-
tinct groups: 1) Ag-rich electrum (>50 at. % Ag); 2) Ag-rich
gold (ca. 25–35 at. % Ag); and 3) Ag-poor gold (<20 at. % Ag).
Crystalline gold
Types 1 and 2 gold possess different chemical composi-
tions. Type 1 gold is composed predominantly of Au, with Ag,
Hg, and Cu either absent or present in trace amounts (Fig. 9;
Table 2). The average composition of this gold approximates
that of virtually pure gold (Tables 1 and 2). Type 2 gold is
composed of Au and Hg, with varying amounts of Ag (Fig. 9;
Tables 1 and 2). Copper was detected in only one analysis
(0.21 at. % Cu).
Origin of the Gold Types
The grain cores are considered primary, thus detrital, in ori-
gin and analogous to the cores of detrital placer gold. The

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 CRYSTALLINE PLACER GOLD, RIO NEUQUÉN, ARGENTINA 627

80
A 100 µm
70
Ag-rich Electrum
60 Grain 1

50

Ag (at.%)
Primary grain core Ag-rich gold
Au-Ag 40
Grain 2
30 Ag-poor
gold
Grain 3
20 Grain 4
Type 1 Grain 5 Grain 6
10
Cryst. Gold
Au
0
20 30 40 50 60 70 80 90 100
B
Au (at.%)
FIG. 8. Bivariate plot of Au versus Ag for primary cores of crystalline gold
grains from the Rio Neuquén, showing intragrain chemical heterogeneity
and average compositions, based on 10 analyses per grain.
Type 1 Cryst. Gold
Au

heterogeneity varies between grains. The variation of both

Primary
Au-Ag core
Type 2
Cryst. Gold
Au-Hg
100 µm
FIG. 7. A. False color back-scattered electron micrograph of a placer gold
grain from the Rio Neuquén, showing distribution of type 1 crystalline gold
and primary grain core. B. Back-scattered electron image of a gold grain from
the Rio Neuquén, showing textural relationship between primary grain core
and types 1 and 2 crystalline gold.
composition of the core is interpreted to reflect the composi-
tion of the primary gold source (Bowles et al., 1984). Based
on multiple analyses of single grains, they are observed to be
heterogeneous in composition, although the extent of the
intra- and intergrain chemical heterogeneity suggests that the
primary grain cores are derived from multiple sources. The
widespread distribution and the various genetic styles of pri-
mary mineralization present in the river’s catchment basin are
consistent with this theory.
The delicate and pristine morphology of the type 1 crys-
talline gold precludes a purely detrital origin for the crystals,
as the individual crystals would not have survived transport;
therefore an authigenic (sensu lato) origin is preferred. Both
type 1 and type 2 crystalline gold are considered to be new
gold crystallized within the fluvial environment. The growth
of the crystalline grains is not interpreted to represent a sin-
gle event, but rather a continual process of gold addition. Ev-
idence for this includes (1) larger crystals overgrowing
smaller ones (Fig. 10A), (2) smaller crystals growing in com-
petition for space with larger ones (Fig. 10B), and (3) crystals
locally covered by a drape of later gold (Fig. 10C, D).
The origin of the microcracks is enigmatic. One scenario is
that they are dissolution marks. However, if this were the
case, they would be expected to be less elongated and more
irregular in shape; thus, a dissolution origin is unlikely.
However, the possibility of subsequent dissolution cannot

TABLE 1. Comparison of Type 1 and Type 2 New Gold from the Rio Neuquén, Argentina

Type 1 Type 2

Morphology Euhedral, crystalline, compact; no spongy texture; Variable, compact irregular protrusions to crystalline;
overgrowths around grain cores, substrate for type 2 gold overgrowths on type 1 gold only

Frequency of occurrence Common Rare

Color when carbon coated Vivid blue Dark red

Composition Virtually pure Au Predominantly Au-Hg amalgam with varying amounts of Ag

Interpretation New gold due to Au addition Hg contamination from historic mining

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628 MCCREADY ET AL.

Ag more than about the outer 2 to 3Å of the gold grain profiles.

Ag They predicted that unreasonably long times (between 1017
30
and 1018 yr) are required for the formation of an 8-µm rim.
However, the results of Groen et al. (1990) are not universally
accepted. Krupp and Weiser (1992) considered that Ag diffu-
30
sion may be accelerated by severe mechanical deformation
Au Hg
(e.g., lattice transformations), and that diffusion may be
quicker along grain boundaries.
Grain Cores When alloyed with less than about three times its own

30
weight of Ag (<ca. 84 at. % Ag), Au will protect the Ag from

at.%
attack (Bowdish, 1983). In commercial refining, this necessi-
tates the dilution of molten natural electrum with two to four

Au
Type 1 Crystalline Gold
Type 2 Crystalline Gold
Au
FIG. 9. Ag-Au-Hg ternary diagram of gold composition (in at. %) of placer
gold from the Rio Neuquén.
be precluded as either a means of widening the cracks or the
cause of some microscale pits present on some crystals.
Formation of Crystalline Gold in the Neuquén System
Here, we consider various mechanisms that may have con-
tributed, either partially or entirely, to the formation of the
types 1 and 2 new gold from the Rio Neuquén. The mecha-
nisms considered are (1) preferential loss of Ag, (2) addition
of new Au, both internally and externally derived, (3) bacte-
rially mediated gold precipitation, (4) deposition from col-
loids and humic substances, and (5) amalgamation by Hg
contamination.
Loss of Ag
A leaching theory does not fully explain how Ag atoms from
deeper than the outer few ångströms of the grains can come
into contact with the leaching solution (Groen et al., 1990).
One possible mechanism is Ag diffusion through the grain.
However, Groen et al. (1990) modeled Ag diffusion profiles
from the interior of gold grains to their surfaces, where disso-
lution can occur. Their calculated profiles suggested that Ag
diffuses much too slowly in AuAg alloys to deplete Ag from
times its weight in Ag (Groen et al., 1990). Yet, the Ag-poor
grain cores (~80–90 at. % Au) from the Rio Neuquén display
overgrowths of type 1 and type 2 new gold. Placer gold grains
from elsewhere in the world, which have a core fineness of
972 and 963, also display distinct rims of 998- and 1,000-fine-
ness gold (Groen et al., 1990; Santosh et al., 1992). This may
Hg be explained in two different ways. One possibility is that nat-
ural processes operating within the placer environments are
different from those encountered in commercial refining. Al-
ternatively, such high Au contents might protect the Ag from
attack. However, there is no evidence to prove or refute ei-
ther possibility.
The sharp nature of the contact between the rim and the
core is difficult to explain in terms of leaching Ag from the
edge of a grain. Bowles (1988) suggests that a leaching
process would presumably give rise to a gradual, rather than
a sharp, transition. The leaching model suggests that any Ag-
poor gold rim would exhibit either (1) a spongy texture (dor-
mant stage of Knight et al., 1999a) or (2) a compact texture
(active stage of Knight et al., 1999a). However, such a model
is not compatible with the occurrence of euhedral crystalline
gold, such as that observed in this study.
Proponents of the leaching model advocate that the growth
of pure, type 1 crystalline gold is not precluded during leach-
ing. However, a leaching origin cannot explain the increased
Hg contents of type 2 crystalline gold (mean Hg content of
6.47 at. %), compared to either type 1 crystalline gold (mean
Hg content of 0.15 at. %) or the primary cores (mean Hg con-
tent 0.09 at. %).
Internally sourced Au
One example of Au addition in which the Au is internally
sourced is “electrorefining.” This is a process whereby a mul-
ticomponent alloy (AuAg) is electrochemically dissolved and
a generally pure phase of the most noble dissolved metal (Au)

TABLE 2. Variation in the Composition (at. %) of Type 1 and Type 2 Crystalline Gold from the Rio Neuquén, Argentina

Type 1 Type 2

Au Ag Hg Cu Au Ag Hg Cu

Minimum 98.12 b.d. (10) b.d. (17) b.d. (21) 89.84 0.19 4.37 b.d. (22)
Maximum 100 0.95 1.88 0.42 95.23 5.07 8.86 0.21
Mean 99.41 0.41 0.15 0.03 92.27 1.25 6.47 0.01
Median 99.22 0.53 b.d. b.d. 92.03 0.83 6.35 b.d.
n 23 23 23 23 23 23 23 23

Numbers in brackets refer to number of analyses in which Ag, Hg, and Cu were below detection; b.d. = below detection

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 CRYSTALLINE PLACER GOLD, RIO NEUQUÉN, ARGENTINA 629

A B
LG
SG

SG

LG

C D
CG

DG
DG

CG
CG DG

FIG. 10. Secondary electron micrographs of crystalline gold from the Rio Neuquén. A. Large authigenic gold crystal (LG)
overgrowing several smaller gold crystals (SG). B. Variation in crystalline gold size. C, D. Smooth drape of gold (DG) par-
tially covering crystalline gold (CG). All scale bars are 10 µm.

is precipitated (Fig. 11; Groen et al., 1990). Such potentials
can be brought about as a result of the electromotive force
between two dissimilar metals in a solution whose Eh is
higher than that in which the starting alloy is stable (self-
eletrorefining, referred to as SERF by Groen et al., 1990).
This AuAg SERF model is analogous to the dezincification of
brass (Fontana, 1986).
The SERF process results in the formation of a series of lo-
bate-shaped protrusions that are composed of redeposited
Au. The shape of these protrusions forms as a consequence of
the surfaces of the more electropositive metal needing to re-
tain sites that are exposed to the aqueous medium, so that dis-
solution and subsequent charge transfer can occur. Hence,
channelways develop between the growing metal deposits on
the surface.
However, several problems exist in applying a SERF model
to the placer gold from the Rio Neuquén: (1) the morphology
of the grains, (2) the occurrence of complete overgrowths,
and (3) the difference in composition between type 1 and
type 2 gold.
The characteristic, lobate-shaped protrusions formed
during the SERF process (Groen et al., 1990) have not been
observed in the type 1 gold from the Rio Neuquén, although
comparable structures have been noted in the type 2 gold. A
SERF process does not permit the formation of overgrowths
that completely engulf the primary grain core, blocking any
access to fresh electrum. In the case of some grains from the
Rio Neuquén, the crystalline gold completely overgrows the
primary core, thus blocking any access to fresh electrum. The
microcracks present on many crystals could be considered as
possible conduits to fresh electrum. However, based upon the
absence of gold crystals around the margin of these microc-
racks, this is considered unlikely. If SERF processes were ac-
tive, the model predicts that gold crystals would be present
around these rims of the microcracks.
Externally sourced Au
Another source of crystalline gold is addition of Au ± Hg
from a source external to the primary grain core, whereby the
Au ± Hg is precipitated onto a preexisting grain core.
Several workers have documented low-temperature aque-
ous transport of alluvial gold in the surficial environment
(e.g., Lesure, 1971; Mann, 1984; Wilson, 1984; Krupp and
Weiser, 1992; Santosh et al., 1992; Abramov et al., 1993, and
references there within; Cidu et al., 1995; Grimes et al., 1995;
Leybourne et al., 2000).
The work of Webster (1986), Groen et al. (1990), Vlas-
sopoulos et al. (1990), Bowell et al. (1993), and Leybourne et
al. (2000) suggests that the effective ligands for the transport
of Au in ordinary stream environments are CN– (cyanide),
OH–, Cl–, thiosulphate (S2O2–3 ), and NH3. The low concentra-
tion of CN– in stream waters suggests that, in the natural

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630 MCCREADY ET AL.
3L2-
(2) (1)
2 AuL- (3)
AgL-
(4)
2 e-
1 e- (5)
e - + 0.25O2 +
0.5H2O => OH -
Au-Ag
Au
Alloy
Corroding Developing Diffusion Bulk
Electrum Au-Rich Rim Boundary Solution
Layer
FIG. 11. Schematic illustration of the self-electrorefining (SERF) process
on the surface of a placer gold grain, entailing the following steps (corre-
sponding numbers on diagram): (1) transport of Au- and Ag-complexing lig-
ands (L2–) to the corroding surface of the placer gold; (2) dissolution of the
gold grain by the complexing agents, with the coincident liberation of three
electrons (e–); (3) loss of the more soluble Ag complex to the bulk solution;
(4) dissociation of the Au complex by reaction with the free electrons at the
pure Au surface, bringing about the precipitation of pure Au; (5) consump-
tion of extra free electrons through reduction of O2 and H2O to OH– (From
Groen et al., 1990).
environment, CN– is unlikely to be a major transport ligand.
However, in environments where previous gold mining em-
ployed the use of cyanide, discharges of cyanide into the flu-
vial system may have occurred, thereby increasing in the con-
centration of CN– in the fluvial system. For example,
Leybourne et al. (2000) identified CN– as the dominant lig-
and in the rivers downstream of the Murray Brook sulfide de-
posit in Canada. The presence of historic mining in the area
suggests that the role of CN– in the Rio Neuquén cannot be
excluded. An externally sourced Au model is highly favored as
a potential mechanism for the formation of the type 1 crys-
talline gold present in the Rio Neuquén, as (1) it does not re-
quire that the original electrum be continually exposed, (2) it
permits the complete engulfment of the parental grain, and
(3) it can account for the lack of textures associated with
SERF.
Bacterially mediated Au precipitation
The role of micro-organisms in the geochemical cycle of
gold has been increasingly considered over the last 30 years
(e.g., Korobushkina et al., 1974, 1976; Boyle, 1979; Watter-
son, 1991, 1994; Knight, 1993). Southam and Beveridge
(1994, 1996) presented mechanistic information about the
0361-0128/98/000/000-00 $6.00 630
role of bacteria in placer gold development. In acid condi-
tions, the uptake of Au from solution was stabilized by bacte-
ria as soluble organogold complexes, and later was reprecipi-
tated extracellularly as crystalline gold. This gold was present
in the form of planar pseudotrigonal (hexagonal)-octahedral
crystals and hexagonal-octahedral crystals up to 20 µm in di-
ameter. The crystals were also observed to aggregate to form
larger (50-µm) grains. These bacterially mediated crystals are
comparable in size to the crystals observed in this study.
One problem with a bacterial origin is that it does not ex-
plain the occurrence of the primary core within the grain.
However, in a more recent study of bacterial activity in Yukon
placer grains, Southam (1998) identified Au or Au-Ag cores
comparable to those from the Rio Neuquén. These cores
were interpreted by Southam (1998) as primary, nonbacteri-
ally derived, unweathered grains, which served as a nucleat-
ing site for the bacterially precipitated Au.
Based on the evidence presented by previous workers, a
bacterial origin cannot be precluded for at least some of the
type 1 crystalline gold within the Rio Neuquén.
Colloidal and humic sources of Au
Humic substances (humic acids, fulvic acids, and humins)
have been suggested to be involved in the genesis of gold
from a variety of mineral deposit types including placer min-
eralization (Wood, 1996). However, disagreement still exists
as to their exact role in gold genesis. One school of thought
(e.g., Friese, 1931; Baker, 1973, 1978; Boyle et al., 1975;
Bergeron and Harrison, 1989; Varshall et al., 1990) is that
humic substances are directly involved in the transport of
gold through complexation. The other school of thought (e.g.,
Fetzer, 1939; Ong and Swanson, 1969; Radtke and Scheiner,
1970; Disnar and Sureau, 1989; Machesky et al., 1992) is that
humic substances are responsible for the fixation of gold, ei-
ther by the reduction and eventual precipitation or by the
binding of Au to humic material.
Wood (1996) suggested that the results of experiments with
humic substances vary for a number of reasons: (1) humic
substances vary widely in composition and structure, even if
they are extracted and treated in an identical manner in dif-
ferent experiments; (2) some nonhumic impurities remaining
within humic substances after extraction (e.g., amino acids)
may be more effective in dissolving Au than were the original
humic acids, especially if they contain both N- and S-donor
groups; (3) variable redox conditions, as humic substances
vary in composition within oxidizing and reducing environ-
ments; (4) the variation in Au solubility due to its preparation,
pretreatment, and grain size or shape; and (5) the degree of
loading of the humic substance by the Au (i.e., since only cer-
tain sites are expected to prefer gold to other ions, these may
become rapidly saturated with gold). In many experiments on
the role of humic acids, the starting gold concentration was
higher than the typical concentration of gold in natural wa-
ters, and, therefore, greater than that which humic substances
are likely to accommodate.
Despite uncertainties surrounding some experiments, it
may be possible for small, but significant, amounts of Au to be
bound to and transported by humic substances. Humins, due
to their natural insolubility in any fluid, can probably be ruled
out in the transport of gold, and furthermore, they would
 CRYSTALLINE PLACER GOLD, RIO NEUQUÉN, ARGENTINA
probably act as reductants if any interaction with Au oc-
curred. A significant role for humic acids is unlikely because
they are only soluble under alkaline conditions, and the pH
range of natural ground and surface waters extends into the
acid field. However, the ability of fulvic acids to remain solu-
ble over a range of pH conditions suggests that they could fa-
cilitate Au transport, particularly if they contain soft binding
sites (S or N).
Seely and Senden (1994) described placer gold from In-
donesia, which they considered to be the result of colloidal
aggregates. Interestingly, the gold has a high fineness
(970–1,000), with much of the gold having a fineness of 998.
The morphology of this gold varies from dimpled plates and
spheres to more crystalline forms, many of which exhibit dis-
crete pyritohedron shapes. The similarities in fineness and
the more crystalline shapes of the gold described by Seely and
Senden (1994) to the high-purity type 1 gold described in this
study suggest that the role of colloids in the formation of type
1 gold cannot be excluded.
Role of mercury
Many of the processes described in this study may explain
the formation of the virtually pure type 1 gold. However,
SERF processes, externally sourced Au, bacterially mediated
Au precipitation, and colloidal gold do not explain the chemi-
cal differences observed between the type 1 and type 2 gold in
the Rio Neuquén. This suggests a role for Hg contamination.
Most Hg found in Au placers is the result of pollution from
the amalgamation process used during Au extraction (Pfeiffer
et al., 1989, 1993; Wayne et al., 1996; Miller et al., 1997), and
Hg is commonly found as an amalgam on Au grains in placer
deposits (Callahan et al, 1992, 1994). McTaggart and Knight
(1993), Knight (1993), and Knight et al. (1999a) suggest that
Hg contamination is the most likely explanation for the new
gold precipitated in placers, and we interpret type 2 gold to
be a result of Hg contamination from historic mining in the
Rio Neuquén area. It remains unclear, however, if type 1 is
also related to Hg contamination, or if it represents gold
formed by one of the mechanisms outlined above. It seems
unlikely that Hg amalgamation was responsible for type 1
gold, because this gold contains virtually no Hg compared to
type 2 gold; the two types of gold have distinctly different
morphologies, and the paragenesis always indicates that the
early type 1 gold is overgrown by later, Hg-rich type 2 gold.
This interpretation is supported by the work of Callahan et al.
(1994), who suggested that Ag-poor rims and Au-Hg amal-
gam in placers contaminated by Hg did not form by the same
process.
Summary of gold formation
Based on the available evidence, we consider that type 1
and type 2 probably formed by two separate mechanisms.
Type 1 is interpreted to be the result of addition of Au from
an external source, rather than leaching or by self-electro-
refining. In contrast, type 2 gold is considered to be the result
of Hg pollution from historic mining in the area.
Analogies and Implications
The chemistry and texture of type 1 new gold strongly sug-
gest that this gold is analogous to the Ag-poor rims present on
0361-0128/98/000/000-00 $6.00 631
631
many placer gold grains. Knight et al. (1999a) consider that
particle movement downstream is not continuous; part of the
time, the gold particles are active (during which time the Ag-
poor rims are probably destroyed), and part of the time, they
are dormant (during which time the Ag-poor rims are thought
to thicken). We believe the crystalline placer gold grains from
the Rio Neuquén represent unique examples of dormant
grains, which do not show evidence of significant abrasion
and peening. The evidence presented in this study supports
the view that Ag-poor rims are the result of Au addition from
an external source, rather than the removal or leaching of Ag
± other elements.
Quantitative morphology, which utilizes the concept that as
grains move downstream they become progressively smaller,
more rounded, and flatter, has been employed by a variety of
workers to numerically describe placer gold, and, in some
cases, applied as an exploration tool to locate the primary
mineralization upstream (e.g., Giusti, 1986; Averill and Zim-
merman, 1986; Sanerbrei et al., 1987; Hérail et al., 1990;
Loen, 1993, 1995; Youngson and Craw, 1999; Knight et al.,
1999a, b). However, this study suggests that failure to recog-
nize the presence of authigenic gold in the sample set would
result in the incorrect interpretation of the data.
The discovery of euhedral authigenic placer gold in the Rio
Neuquén suggests that the simple interpretation that
“rounded grains indicate detrital” and “euhedral grains indi-
cate hydrothermal” may not always be correct. Such a view
has been suggested by some who propose a hydrothermal ori-
gin for the free gold in Witwatersrand deposits (e.g., Barni-
coat et al., 1997a, b).
Conclusions
The crystalline gold from the Rio Neuquén, Argentina, is a
rare example of placer gold, the morphology and chemistry of
which are interpreted to reflect derivation from multiple
sources. Two distinct types of crystalline gold are recognized:
1) virtually pure gold, and 2) an AuHgAg amalgam. The AuH-
gAg amalgam (type 2 gold) is interpreted to be due to conta-
mination from historic mining. In contrast, the virtually pure
type 1 gold is interpreted to represent an example of new gold
that originated from the addition of Au from an external
source. Type 1 new gold from the Rio Neuquén is interpreted
be analogous to the Ag-poor rims present on most placer gold
grains. The evidence presented in this study supports the
view that the Ag-poor rims are the result of Au addition and
not Ag removal or leaching.
Acknowledgments
The financial support for the fieldwork was provided by the
University of Buenos Aires (UBACYT-JX 18). The analytical
work for this project was funded by the Queen’s University of
Belfast as part of a N.I. Dev. R. Postgraduate award. Techni-
cal assistance from the staff of the Queen’s University Elec-
tron Microscope Unit, and G. Alexander and M. Pringle are
also gratefully acknowledged. The manuscript benefited
greatly from the reviews by John Youngson, an anonymous re-
viewer, and Mark Hannington.
June 26, 2000; December 13, 2002
632 MCCREADY ET AL.
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