197Au MSssbauer Study of Copper Refinery Anode Slimes

J.A. SAWICKI, J.E. DUTRIZAC, J. FRIEDL, F.E. WAGNER, and T.T. CHEN
Copper refinery anode slimes are abundantly produced during the electrolytic refining of copper.
Although the slimes contain significant and economically recoverable amounts of gold and silver, the chemical state of the gold has not been fully identified. In the present work, the chemical form of gold in a copper anode, in a raw slime, and in slimes treated by different leaching
procedures has been investigated by Mrssbauer spectroscopy with the 77.3 keV y-rays of 197Au.
The Mrssbauer spectrum of the anode is typical of a dilute Au:Cu alloy. The spectrum of the
raw slime consists of two components, namely, a single, rather broad line with an isomer shift
(IS) of about - 0 . 3 m m / s relative to a Pt metal source and a quadrupole doublet with an IS of
+ 1.2 m m / s and a quadrupole splitting of 5.0 mm/s. The single line component can be attributed to a gold-rich alloy, with an approximate composition of Au60Ag40 or AusoCu20 if it is a
binary alloy, or to a ternary Au-Ag-Cu alloy of appropriate composition. The parameters of the
quadrupole doublet match those of Ag3AuSe2 (fischesserite) or related Ag2_xAuxSe compounds.
In these compounds, the gold atoms are coordinated by two selenium atoms in a linear arrangement, as is typical for Au(I). It was found that the ratio between the concentrations of the
metallic phase and the selenide strongly depends on the leaching conditions. The measurement
of the Lamb-Mrssbauer factor of fischesserite is also reported.

I.

INTRODUCTION

THE world's annual output of primary copper is nearly

9,000,000 tons, and approximately 80 pct of the output
originates from the smelting of copper sulfide concentrates. In addition, large amounts of copper are recycled,
either by the primary producers or by secondary
smelters/refiners, m Copper sulfide concentrates commonly contain important concentrations of Au and Ag.
Many secondary feeds, especially electronic scrap, are
also rich in Au, Ag, Pd, etc. Both primary and secondary smelting operations efficiently collect the precious
metals, which report nearly quantitatively to the blister
copper product of the smelting operation. The blister
copper, which contains - 9 8 pct Cu, is fire refined, and
the fire-refined copper is cast into anodes. Subsequently,
the anodes are electrorefined at approximately 65 ~ in
an electrolyte containing 45 g / L Cu and 160 g / L H2SO 4.
This yields copper cathodes of 99.99 pct purity, which
can be cast into rods with market specifications for ductility and electrical conductivity. The impurities present
in the anode either dissolve and accumulate in the electrolyte or form an insoluble anode slime, which collects
both on the anode face and the cell bottom.
Commercial copper anodes often contain up to 100
ppm Au, although higher gold contents have been occasionally noted. 121The gold is concentrated in the anode
slimes, from which it is recovered as a valuable byproduct. The first step in the treatment of the anode slimes
is "decopperizing," wherein Cu, Ni, and Te are selectively dissolved to concentrate Au and Ag in the leach
J.A. SAWICKI, Research Scientist, is with AECL Research, Chalk
River Laboratories, Chalk River, ON KOJ 1JO, Canada. J.E.
DUTRIZAC and T.T. CHEN, Research Scientists, are with Energy
Mines and Resources Canada, CANMET, Ottawa, ON K1A OG1,
Canada. J. FRIEDL, Student, and F.E. WAGNER, Professor, are
with Physik-Department El5, Technische Universit~it Munchen,
D-8046 Garching, Germany.
Manuscript submitted September 3, 1992.
METALLURGICAL TRANSACTIONS B

residue. Selenium is next eliminated by a selective volatilization process at elevated temperature. The resulting
Au- and Ag-rich product is smelted to yield an Au-Ag
alloy for further refining. The initial "decopperizing" step
is sometimes carried out in air-agitated tanks at ambient
pressure, although the process is more effectively conducted using O2 at elevated temperatures and pressures
in an autoclave. The success of the "decopperizing" process and the reactions that occur in that step impact significantly on the remainder of the anode slime treatment
process.
In many refineries, the value of the gold by-product
is 25 to 50 pct of that of the produced copper.t2'3] Despite
the economic importance of gold to the copper refining
industry, the behavior of this element during electrorefining is not well understood. There are uncertainties
concerning the form of Au in both the as-cast anodes
and the anode slimes, and the reactions of gold in the
refining cells are largely speculative. Because a knowledge of the forms of Au could impact directly on the
processing options for Au recovery from the anode slimes,
various mineralogical studies have been undertaken. [3'4]
These studies indicated that Au in the anode slimes occurs
as < 1 /xm grains of metallic gold and as tiny particles
of Au-Ag-Cu selenide. The small particle sizes of the
gold carriers precluded a definitive mineralogical characterization, and thus, recourse was taken to Mrssbauer
methods to confirm the mineralogical observations and
to shed additional light on the gold phases present.
Mrssbauer spectroscopy of the 77.3 keV y-rays in 197Au
has been used for the characterization of gold compounds, 15,6,71 alloys, t8,91 and more recently, gold
minerals. [10,11,12]

II.

EXPERIMENTAL TECHNIQUE

A. Materials

A commercial copper anode (sample 1) and an airdried raw anode slime were obtained from the copper
VOLUME 24B, JUNE 1993--457

refining operations of the CCR Refinery of Noranda

Copper Smelting and Refining, Montreal, PQ Canada.
The refining was performed at 65 ~ in electrolyte containing 150 g / L H2SO 4 and 45 g / L Cu as CuSO4. The
slimes typically represented 0.5 to 1 wt pct of the refined
copper product. The leaching of the slimes was performed in the laboratory using actual industrial solutions, which were also obtained from CCR. The raw anode
slime (sample 2) was leached for 3 hours at 25 pct solids
in 250 g / L H2SO 4 at 115 ~ and 300 kPa O2 partial pressure and subsequently for 2 hours in 250 g / L H2504 at
180 ~ and 700 kPa 02 partial pressure (sample 3). The
raw anode slime was also leached in a single step at
115 ~ and 700 kPa 02 partial pressure in a solution
containing 250 g / L H2SO4 and 10 pct NaC1 (sample 4).
Finally, an unspecified raw anode slime, different from
sample 2, was leached in 250 g / L H2SO4 for 3 hours at
150 ~ and 300 kPa 02 partial pressure to generate sample 5. In addition to the components specified above, the
leaching solutions also contained 25 to 50 m g / L of chloride ion, together with 1 to 2 m g / L of thiourea. A mineralogical study of the various anode slime samples
showed them to consist principally of AgzSe, AgCuSe,
PbSO4, BaSO4, Ag2SO4, AgC1, and silicate species; details are available in the literature, t131
The bulk chemical compositions of the various materials are given in Table I; note that the elemental compositions do not sum to 100 pct. This is a consequence
of the fact that anode slimes also contain a number of
minor elements, such as As, Sb, Bi, S, etc. Furthermore, many of the impurities occur in oxidate form (arsenate, sulphate, antimonate, etc.), and some of the
oxidate phases are themselves hydrated.

spectra proved to be difficult because of the low content

of Au and the high content of heavy elements, mainly
lead. All measurements were performed in a transmission geometry. The 18-hour half-life 197pt sources for the
197AH M6ssbauer measurements were prepared by irradiation of about 200 mg of enriched 196pt metal in a nuclear reactor for about 1 day, the neutron flux being
2 x 10 ~3 n. s -~ cm -2. The Mrssbauer y-rays were detected with a planar intrinsic Ge detector, which yielded
count rates of up to 2 x 105/s in the window of
the single-channel analyzer set on the 77.3 keV line.
The absorber thickness was between about 1.9 and
3.3 g / c m 2. All measurements were performed with both
the source and the absorber cooled to 4.2 K in a liquid
He cryostat. The spectra were least-squares fitted with
superpositions of Lorentzian lines. All line positions and
isomer shifts (ISs) are given with respect to the source
of 197Au in Pt metal. To convert them to shifts relative
to metallic gold, 1.23 m m / s must be added to the given
values.
III.

A. Mineralogical Observations
Although the copper anode was extensively examined,
no discrete gold phases were detected. In particular, no
Au-bearing selenides were found, and electron microprobe analysis of many of the copper selenide particles
did not detect gold at the 250 ppm Au minimum detection limit. No inclusions of metallic gold were observed,
and gold rims on other inclusion phases were not evident. Proton-induced X-ray emission analysis (PIXE) of
the copper metal matrix consistently detected Au in solid
solution in the copper. Although the analytical errors associated with this technique make a definitive statement
about the deportment of Au in the anode difficult, the
implication is that all of the gold occurs in solid solution
in the copper metal matrix.
Two gold-bearing phases were detected during the
mineralogical study of the raw anode slimes. The most
common occurrence is <1 /xm spikelike gold grains,
which are commonly attached to particles of Ag-Cu selenide. These grains appear to form during the electrolytic dissolution of the anode from the gold originally in
solid solution in the copper. [3.15] As the copper dissolves
electrochemically, gold becomes concentrated at the surface of the anode. Eventually, a gold phase nucleates
from the Au-Cu solid solution and grows into the small
spikelike particles visible in Figure 1. The SEM-EDX

B. Mineralogical Methods
The anode slimes were examined in a scanning electron microscope equipped with an energy-dispersive X-ray
analyzer (SEM-EDX) to determine the phases present.
The wavelength-dispersive spectrometer of the electron
microprobe was used to locate Au-rich regions, which
were then examined in detail by the SEM-EDX system.
Where possible, the electron microprobe was used to estimate the compositions of the Au-bearing phases. Details of all of the mineralogical methods were recently
reported. [14]

C. Mdssbauer Spectroscopy
Mrssbauer spectroscopy of the 77.3 keV y-rays in 197Au
was used to determine the chemical form of gold in the
anode and anode slimes samples. Obtaining high-quality

Table I.

Sample
1. Copper anode
2. Raw anode slimes
3, H2SO4 leached
4. HzSO4/NaC1 leached
5. H2SO4 leached at 150 ~
(--) Not analyzed.
458--VOLUME 24B, JUNE 1993

RESULTS AND DISCUSSION

Compositions of the Anode and Anode Slimes Samples (Weight Percent)

Cu

Ag

Se

Te

Ni

Pb

SiO2

Ba

Au

Pt

Pd

-99
13.2
0.05
0.12
0.05

0.21
21.2
21.4
24.2
36.9

0.11
9.9
5.9
13.0
13.8

-1.3
0.7
0.7
1.3

0.13
0.4
0.01
0.08
0.03

0.05
--20
15.2
15.6
11.1

--5.7
4.0
--

--0.9
0.6
--

0.006
0.51
0.99
0.82
4.06

--0.03
0.03
--

--0.35
0.30
--

METALLURGICAL TRANSACTIONS B

to 12.5 pct Au, 30.5 to 37.7 pct Ag, 8.8 to 14.5 pct Cu,
and 21.2 to 25.2 pct Se. There is a large analytical uncertainty in the electron microprobe analyses because of
the very small size of the gold selenide particles. Nevertheless, the data suggest an approximate formula of
Au(Ag,Cu)sSes; i.e., M2 xSe. Also, a Ag3AuSe2 phase
(fischesserite) was detected in sample 5 by both X-ray
diffraction analysis and S E M / E D X study.
The gold-containing selenide phase does not seem to
occur in the copper anode. This suggests that the gold
present in alloy form in the anode dissolves and then
diffuses a short distance into the anode slime layer, where
it reacts with the selenide particles to make the AuAg-Se selenide phase (Eqs. [1] through [3]). This limited degree of Au mobility has important ramifications
for the understanding of the copper refining process.
Fig. l - - B a c k s c a t t e r e d electron micrograph of several tube like particles of AgCuSe in the raw anode slimes. Several < 1-/xm spikelike
gold grains (arrows) are attached to the surface of the selenide (loose
powder mount).

analysis indicated that these particles consist of Au with

minor Ag and Cu contents. Because of the small size of
the particles, however, it was not possible to ascertain
whether the Ag and Cu are in solid solution in the gold
or whether these elements were detected because of secondary fluorescence from the adjacent Ag-Cu selenides,
which are typically AgCuSe or copper-bearing Ag2Se.
Gold also occurs in selenide form in the anode slimes.
In addition to Au-rich areas in the Ag-Cu selenides, a
number of particles of a Au-Ag-Cu selenide phase were
detected. The Au-Ag-Cu selenide is associated either with
Ag-Cu selenides or with a complex precipitated oxidate
phase consisting of an intimate mixture of Ag, Cu, and
Pb sulfates, selenites, and arsenates, t31 Figure 2 shows a
porous mass of the oxidate phase, which is intergrown
with fragments of Ag-Cu selenide. The bright 2- to
3-1xm2 area is a gold-bearing selenide. Electron microprobe analysis of the gold-bearing selenide indicated 12.1

Fig. 2 - - Backscattered electron micrograph of a porous mass o f precipitated oxidate phase present in the raw anode slimes. The bright
phase marked by the arrow is Au-Ag-Cu selenide (loose powder mount).
METALLURGICAL TRANSACTIONS B

B. MiSssbauer Observations

The information about the chemical state of gold obtained by Mrssbauer spectroscopy stems mainly from
electric quadrupole interaction and from the IS of the
Mrssbauer pattern. The former splits the Mrssbauer line
of 197Auinto a doublet whose separation, the quadrupole
splitting (QS), depends on both the symmetry and the
degree of covalency of the bonds between the gold atoms
and their ligands. The IS is a measure of the electron
density at the gold nuclei. Both the electron density at
the gold nuclei and the IS increase with the valence state
of gold and with the covalency of the bonds between
gold and its ligands. For the linear twofold coordinated
Au(l) compounds, as well as for the planar fourfold coordinated Au(III) compounds, distinctive and approximately linear correlations between the electric QS and
the IS have been found. [6.7] Using these correlations, the
valence state of gold in such compounds can be determined from the observed values of the IS and the QS.
For bonding situations that deviate from the twofold linear or fourfold planar coordination, however, a distinction between Au(I) and Au(llI) on the basis of Mrssbauer
spectroscopy is difficult, the more so since the sign of
the electric quadrupole interaction, which is expected to
be negative for linear Au(I) and positive for planar Au(ILI)
compounds, 171 cannot normally be determined.
The 197Au MOssbauer spectrum of the copper anode
containing 61 ppm Au is shown in Figure 3. The absorber used in this measurement had a thickness of 1.9
g / c m 2 of the anode material. The spectrum consists of
a single, broadened line at +2.79 mm/s. This value is
in good agreement with the value of the IS for an alloy
of 1 at. pct Au in Cu (Table II and Figure 4). The spectrum of the anode presumably represents gold dissolved
in the copper matrix but associated with other impurities
that cause both the line broadening (W = 2.88 m m / s for
the anode vs W = 2.02 m m / s for the reference 1 at. pct
Au in Cu alloy). No other form of gold, and in particular
neither unalloyed metallic gold nor gold selenides, could
be detected in the M6ssbauer spectrum of the anode material within the statistical accuracy of the measurement.
This finding is in agreement with the mineralogical
observations.
The 197Au Mrssbauer spectra of the four anode slime
samples studied are shown in Figure 3, and the relevant
VOLUME 24B, JUNE 1993--459

~176

~ 9

* **

*** **

9 ~

9 . 9

.....

o
o

~
o

_
~

99.96-

*o

o
o

#1

9
o

100-

M 6 s s b a u e r parameters are c o m p i l e d in Table II. The

spectra of the different slime specimens exhibit two wellseparated absorption lines. The fight-hand p e a k is alw a y s at virtually the same position, + 3 . 7 2 -+ 0.02
m m / s , and has nearly the natural linewidth o f 1.89
m m / s . The left-hand peak is more intense and broadened
in the spectra o f specimens 2 and 3. This suggests that
it is c o m p o s e d o f the left p e a k o f a quadrupole doublet
attributable to Ag3AuSe2 or a related c o m p o u n d and a
peak due to a g o l d - s i l v e r , g o l d - c o p p e r , or gold-silverc o p p e r alloy. The M 6 s s b a u e r spectra o f these samples
was therefore d e c o n v o l u t e d a s s u m i n g a s y m m e t r i c a l
q u a d r u p o l e d o u b l e t and a single line, which turned out
to be substantially b r o a d e n e d . F o r the raw anode slime,
this line has an IS o f - 0 . 3 + 0.1 m m / s , a line width
o f 2.9 _+ 0.5 m m / s , and a fractional area o f 27 -+ 3 pct.
The second c o m p o n e n t is a quadrupole doublet with an

99.7-

--.,

100

100

.o
o

?.
"~

92

99. #3

100'

lO0 . . . .

**. r~-"~'-~w-"

oo

=
O

99.

99.4"

"4~

#4

t~
o

100
o

99
99.6o

Velocity (ram/s)
197

Fig. 3 - - Au M6ssbauer spectra of the copper anode (1), unleached

(raw) anode slime (2), H2SO4 leached slime (3), HzSO4-NaC1 leached
slime (4), and slime I-I2SO4 leached at 150 ~ (5).

460--VOLUME

2 4 B , J U N E 1993

:8

6
Velocity ( r a m / s )

Fig. 4--197Au MOssbauer spectra of some reference materials: Aumetal, fischesserite Ag3AuSe2, and 1 pct Au:Cu.
METALLURGICAL TRANSACTIONS B

Table II.

Mssbauer Results for the Investigated Copper Anode, Anode Slimes, and Some Reference Materials*

Sample
1. Copper anode
2. Raw anode slime
3. H2504 leached
4. H2SOa/NaC1
5. H2SO4 leached at 150 ~
6. Ag3AuSez synthetic
7. Agl.sAu0.2Se
8. 1 at. pct Au in Cu
9. 1 at. pct Au in Ag

IS
(ram/s)

QS
(ram/s)

W
(mm/s)

RI
(pct)

CA~
(pct)

+2.79(10)
+1.22(4)
-0.30(10)
+1.18(9)
-0.91(7)
+1.23(2)
0.46(29)
+ 1.27(2)
+1.20(1)
+1.28(5)
+2.79(2)
+2.75
+0.68(1)

-5.03(6)
-5.13(16)
-5.02(4)
-5.14(3)
4.96(3)
4.99(5)
--

2.88(44)
2.03(10)
2.94(50)
1.91(14)
2.27(15)
1.99(65)
1.99
2.10(4)
1.94(2)
2.08(8)
2.02(4)

100
73(3)
27(3)
44(3)
56(3)
97(1)
3(1)
100
100
100
100

88.5
11.5
69.2
30.8
98.6
1.4
100
100
100
100

--

1.90(4)

100

100

Identification
Au in Cu
Ag3AuSe2**
Au59Ag41or Au76Cu23
Ag3AuSe2**
Au86Ag14 or Au92Cu8

Ag3AuSe2**
Au26Ag74 or AussCu42
Ag3AuS%**
References 11, 12, 20
Reference 19
this work
Reference 8
this work

*IS is the isomer shift relative to the source of Au in Pt metal; QS, the electric quadrupole splitting; W, the FWHM line width; RL, the
relative intensity of the respective components in the Mrssbauer spectra; and CAothe relative concentration of gold in the different phases. Figures
in parentheses indicate the uncertainty in the last digit(s) reported.
**Related Ag-Cu-Se selenides are also possible.

IS of +1.22 --- 0.04 m m / s , a QS of 5.03 -+ 0.06 m m / s ,

a line width of 2.0 -+ 0.1 m m / s , and a fractional area
of 73-+ 3 p c t .
Within the limits of error, the parameters of the quadrupole doublet match those of Ag3AuSe2,1~1'1~'2~ the mineral fischesserite t~6'17'~81)or of AgLsAu0.zSe 1~91(Table II).
In both compounds, the gold atoms are coordinated by
two selenium atoms in a linear arrangement, as is typical
for Au(I). I5'6'71 However, all (Au,Ag,Cu)2Se-type compounds containing linearly coordinated Se-Au-Se entities may give very similar Mrssbauer parameters and,
hence, may be nearly indistinguishable by Mrssbauer
spectroscopy.
The single line component can be attributed to a goldrich alloy, whose average composition can be estimated
from the ISs of the Au-Ag and Au-Cu alloys LS~to be near
Au6oAg40 or AusoCu20 if it is a binary Au-Ag or Au-Cu
alloy. The composition of gold-silver and gold-copper
binary alloys can be estimated using an empirical linear
relationship between the content of silver or copper, x,
in Au~00-xAgx or Au~0o-xCux alloys and the IS of the
Mrssbauer line, I8'91which can be written as x[at. pct Ag]
= 4 4 . ( I S [ r a m / s ] + 1.23) and x[at. pct Cu] =
2 5 - ( I S [ r a m / s / + 1.23), respectively. The compositions
given in Table II have been derived from these relations
and the observed ISs. Equally, however, the alloy could
be a ternary solid solution of Au-Ag-Cu. Experimental
data for ternary Au-Ag-Cu alloys do not exist, but it appears reasonable to assume a linear superposition of the
influence of Cu and Ag admixtures to gold, at least for
low Cu and Ag concentrations. A ternary Au-Ag-Cu alloy
of appropriate composition should therefore also yield
the observed line position. The large linewidth indicates
that there is a considerable spread in alloy composition,
as reported in the PIXE studies) 3J
The relative intensities of the individual components
in the Mrssbauer spectrum do not represent directly the
relative amounts of gold present in these components,
since the recoil-free fractions or L a m b - M r s s b a u e r f factors, will be different for gold in different chemical states.
In order to account for this, the ratio of the f factors of
METALLURGICAL TRANSACTIONS B

Au in Ag3AuSe2 and in metallic gold was measured by

a reference absorber technique, which implies measuring
the M6ssbauer spectrum of an absorber consisting of
known amounts of Ag3AuSe2 and metallic gold. From
the relative line intensities in such a spectrum, the ratio
f(Ag3AuS%)/f(Au metal) = 0 . 3 5 ( 1 ) w a s obtained. The
relative amounts of gold in fischesserite and in the goldsilver alloy, CAn, (Table II) were determined, taking the
different f factors into account and assuming that the f
factor of the alloy phase is the same as that of pure Au.
Although the above interpretation is generally correct, it
should be noted that the selenide phase may have a composition somewhat different from that of fischesserite and,
accordingly, that a somewhat different f factor may be
involved.
In the raw anode slime, 11.5 pct of the gold is thus
present in the form of Au-Ag, Au-Cu, or Au-Ag-Cu alloys, whereas 88.5 pct is chemically bound in Ag3AuSe2
or related selenides. The 30.8 pct relative amount of metallic gold in the H2SO4 leached anode slime (sample 3)
is nearly three times larger than in the raw anode slime.
In this material, the metallic gold contains less Ag or Cu
than in the raw slime. Also, the M6ssbauer line is narrower, which means that the distribution of compositions
is not as broad as in the raw slime. The H 2 5 0 4 + NaC1
leach (sample 4), on the other hand, eliminated the metallic fraction almost totally, leaving practically all of the
gold in selenide form, possibly fischesserite. The H2SO4
leach at 150 ~ (sample 5) converted all the gold to goldsilver selenide, confirming the mineralogical observations.
The fact that more gold occurs in metallic form after
the H 2 S O 4 leach in sample 3 than in the starting material,
sample 2, suggests that some of the gold bound in the
selenides is liberated when the gold-containing copper
selenides are leached. The gold formed in this way contains less silver and/or copper than the metallic gold in
the raw slime. Possibly, silver and/or copper are also
leached from the tiny alloy crystallites already present
in the raw slime, shifting the M6ssbauer spectra toward
more negative velocities.
VOLUME 24B, JUNE 1993--461

On the other hand, leaching in a H 2 S O 4 q- NaC1 solution converted virtually all of the gold into selenide
form. Although gold is considered to be insoluble in sulfuric acid media, the presence of chloride could cause
some solubility of that element under oxidizing conditions and its subsequent precipitation as a gold-silver selenide. Although speculative, the reactions involved could
be of the generalized type
Au + 0.2502 + H + ~ Au + + 0 . 5 H 2 0

[1]

Au + + L - ~ AuL

[2]

AuL + 2AgzSe--> Ag3AuSe 2 + Ag + L

[3]

where the ligand L would be chloride in the present case

but could, for instance, also be thiourea, which is added
together with glue and chloride to the electrolyte in the
copper cell house to improve the copper deposit quality.
In the industrial leaching process, the refinery electrolyte
is also used in the slimes leaching circuit, and the refinery electrolyte typically contains 25 to 50 m g / L chloride
ion. Hence, the above reactions may also occur in the
industrial process.
Only gold chemically bound in selenide form was observed in the slime leached in H z S O 4 at 150 ~ The
absence of a metallic gold fraction in sample 5 may be
attributable to the different composition of this slime, as
all of the slime samples were leached in industrial electrolyte containing 25 to 50 m g / L chloride ion, together
with lesser amounts of thiourea.

IV.

CONCLUSIONS

The 197Au Mrssbauer analysis of a copper anode revealed only gold in solution with copper, but the gold
seems to be associated with other impurities. All of the
studied anode slimes contained fischesserite, Ag3AuSe2,
or a related selenide possibly also containing copper, in
addition to a gold alloy component. Further Mrssbauer
work on well-characterized Au-Ag-Cu selenides is needed
to decide whether, or to what extent, Mrssbauer spectroscopy can distinguish between different compounds of
this type.
The presence of gold-silver selenides in the slimes
conf'u-ms earlier mineralogical observations. It was found
that the ratio between the concentrations of the metallic
phase and of fischesserite strongly depends on the leaching conditions. The Mrssbauer results suggest that metallic gold dissolves during the leaching of the anode
slimes and that dissolved gold reacts with preexisting

462--VOLUME 24B, JUNE 1993

Ag2Se to form a fischesserite-like compound. These reactions could certainly be clarified by the M6ssbauer
method from more systematic laboratory leaching experiments carried out on more Au-rich slimes.

ACKNOWLEDGMENTS
The authors would like to thank the CCR Refinery of
Noranda Copper Smelting and Refining and the Noranda
Technology Centre for supplying the samples used in this
study, for providing information on the samples, and
for encouraging the publication of this work. This work
has been funded,
in part, by the Deutsche
Forschungsgemeinschaft and AECL Research.

REFERENCES
1. K. Gockmann: CIM Bull., 1992, vol. 85, p. 150.
2. J.H. Schloen: The Electrorefining and Winning of Copper, J.E.
Hoffmann, R.G. Bautista, V.A. Ettel, V. Kudryk, and R.J.
Wesely, eds., TMS, Warrendale, PA, 1987, p. 3.
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METALLURGICAL TRANSACTIONS B