Hydrometallurgy 177 (2018) 79–85

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Use of amino acids for gold dissolution T

a,⁎ b
C.G. Perea , O.J. Restrepo
a
Group of Environmental Geochemistry, Pedagogical and Technological University of Colombia, Sogamoso, Colombia
b
Institute Of Minerals CIMEX, School of Mines, Universidad Nacional de Colombia, Medellin, Colombia

A R T I C L E I N F O A B S T R A C T

Keywords: As oxidants under alkaline conditions. To analyze the kinetics of leaching, tests were performed using electrical
Gold leaching contacts pins and sheets of pure gold to avoid the effects of pore diffusion. The efficiency of each oxidant was
Cyanide alternatives evaluated, for concentrations of 0.004, 0.01 and 0.03 M, at pH values of 9.4 and 11. At the end of each test, the
Organic solvent solid residue was analyzed to determine the total grade and percentage of metal extraction. The experimental
results indicated that the percentage of gold extraction was affected by the oxidant concentration and the pH.
Furthermore, it improves with the presence of Cu2+ ions, increasing by 100% for glycine and approximately 6
fold for glutamate as compared to glycine solutions. In assessing the percentage of gold extraction in the different
conditions at 25 and 40 °C, it was observed that the kinetics of extraction is sensitive to temperature change,
which suggests that the leach is chemically controlled.

1. Introduction
The extraction of gold from its minerals is achieved through hy-
drometallurgical processes, where the traditional process of cyanida-
tion has dominated. Since the beginning of the 20th Century, the ac-
ceptance of cyanidation by gold producers is a tribute to its
effectiveness (Avraamides, 1982). As a process, it has resisted economic
difficulties imposed by the fall in the price of gold, and the introduction
of Carbon in pulp (CIP), has tended to make it even more attractive as a
leaching system.
The main disadvantage of cyanidation is its toxicity. The environ-
mental problems associated with the leakage of cyanide into ground-
water systems and the health risks inherent in the use of this on any
scale are a strong drawback (Avraamides, 1982). Furthermore, its in-
stability, its high affinity with other elements, the decrease easily ex-
tracted gold and the presence of refractory minerals that are not sus-
ceptible to cyanide, sometimes cause relatively high operating costs.
(Poisot, 2010).
For that reason, there is a clear need to implement clean technol-
ogies for the extraction of silver and gold, that increase productivity by
avoiding the generation of waste contaminants (The corral, 2003). The
scientific community has proposed alternative hydrometallurgical
processes for the dissolution of these precious metals using thiosul-
phate, thiourea, chlorine, thiocyanate, among others. An alternative
route could employ other organic ligands, that can compete with the
cyanidation in cost, performance and effectiveness (Guzmán, 2013;
Galindo, 2013).
In this study, a method was evaluated for the recovery of gold from
computer contact pins and a sheet of pure gold, using alkaline solutions
of amino acids such as glycine and monosodium glutamate. The se-
lection of these reagents was based on a review of scientific literature
(Aylmore, 2005; Eksteen and Oraby, 2015a,b,c), where the former
conducted a review of different methods of gold leaching as an alter-
native to cyanidation, mentioning the dissolution with amino acids and
using as potassium permanganate oxidizing agent. Meanwhile Eksteen
and Oraby performed the leaching of metallic gold using amino acids
such as glycine, alanine and histidine at low concentrations, in alkaline
solutions with hydrogen peroxide (H2O2), evaluating the influence of
reagent concentration, temperature and presence of sulphide minerals
in the rate of leaching.
This methodology could represent an alternative to cyanide for gold
recovery and could diminish the environmental impacts generated by
the inadequate handling of the compounds used for gold beneficiation.
Oraby and Eksteen (2014) also evaluated the extraction of copper and
gold from a copper concentrate employing glycine; their results show a
copper extraction of nearly 96%. However, a very low content of gold
was found in solution, using hydrogen peroxide at pH values between 8
and 11. The reactions below indicate a strong affinity of copper with
glycine, both in the cuprous as well as cupric oxidation states:
Cu2 + + 2(H2 NCH2 COO)− ↔ Cu(NH2 CH2 COO)2 , Log10K = 15.6 (1)
Cu+ + 2(H2 NCH2 COO)− ↔ Cu(NH2 CH2 COO)−2 , Log10K = 10.1 (2)
Therefore, further study is warranted to evaluate the ability of

⁎
Corresponding author.
E-mail address: cgpereas@unal.edu (C.G. Perea).

https://doi.org/10.1016/j.hydromet.2018.03.002
Received 28 August 2017; Received in revised form 22 February 2018; Accepted 1 March 2018
Available online 20 March 2018
0304-386X/ © 2018 Published by Elsevier B.V.
C.G. Perea, O.J. Restrepo Hydrometallurgy 177 (2018) 79–85

amino acids in general, not only to enhance, but to completely replace H 2 (Gly)+ H(Gly) Gly−
1.0
cyanide as a ligand for gold extraction. In the present work, two amino
acids, glycine and glutamate, were employed.
0.8
2. Materials and methods

All leaching experiments were carried out using pins from compu- 0.6
ters and thin gold sheets, to avoid the effects of pore diffusion, common

in mineral, and to evaluate gold dissolution with these selected amino
acids. The pins are electrical contacts, composed of gold-plated metal
alloys. Therefore, these pins, due to its characteristics and its relatively
low cost, became the ideal material to assess the conditions in which
gold dissolves in aqueous solutions of these organic ligands (amino
acids). The results obtained with the pins were compared with two tests
performed on samples cut from a pure gold sheet (99.95%, Sigma-
Aldrich). The organic ligands (glycine and glutamate) and oxidizing
agents (hydrogen peroxide (30% w/v) and potassium permanganate)
employed in this work were of analytical grade. For pH adjustment,
NaOH was used.
The pins were characterized by scanning electron microscopy SEM-
EDX (ZEISS EVO MA10), in order to estimate the chemical elements
present and their distribution. A sample of these was digested in a
mixture of nitric acid and hydrochloric acid, later the elemental com-
position of this solution was determined by using atomic absorption
spectrophotometry (Varian SpectrAA 220fs).
The pins were subjected to a pre-treatment, which consisted in the
placement of 5 g of pins into 200 ml of 1.8 M H2SO4 and 7.8 M H2O2
aqueous solution for 3 h, mixing at 300 rpm, to eliminate the presence
of other metals that might affect the gold leaching process. The filtered
residue contained mainly gold.
Leaching experiments of the residue were performed in aqueous
solutions of 0.5 M glycine or glutamate, with potassium permanganate
or hydrogen peroxide as oxidizing agents (Eksteen and Oraby,
2015a,b,c). Liquid samples of 0.5 ml were drawn at 1, 2, 4, 6, 23 and
24 h. Each of the samples was filtered and analyzed to determine the
gold content in solution by the atomic absorption spectrophotometer.
In Table 1 is shown the conditions of the leach test, where the pH
value of 9.4 was selected based on the thermodynamic analysis (see
below), while the pH 11 and the initial concentration of oxidizing agent
to the 0.03 M was based on previous work (Eksteen and Oraby,
2015a,b,c) (Aylmore, 2005). Once the leach time was completed, the
solution was filter and the leach residue was digested using a mixture
nitric and sulfuric acids, which was analyzed by atomic absorption
spectrophotometry, to determine the final gold content and to carry out
the mass balance.
Fraction
0.4
0.2
0.0
0 2 4 6 8 10 12 14
pH
Fig. 1. Species distribution diagram as a function of pH for glycine at 25 °C,
[Gly] = 0.5 M.
Oraby (2015a,b,c). No value was found for the gold-glutamate complex;
given its chemical similarity to glycine (glutamate has an additional
carboxylic group), similar behavior can be assumed.
In Fig. 1 is presented the species distribution diagram for 0.5 M
glycine as a function of pH. At alkaline pH, the dissociation of the
glycine increases, thus achieving the highest concentration of glycinate
available to form complexes with gold or any other metal.
Aylmore (2005) reported a log10 (stability constant) of 18 for the
gold (I) - glycine complex. In Fig. 2 is shown the diagram of thermo-
dynamic stability Eh-pH for the gold-glycine at room temperature in
0.5 M of glycine. As may be noted, the elemental gold is the species
stable at all values of pH and potential under 0.5 V; for higher values,
there is a zone of stability for the formation of the complex gold-gly-
cine, although the lowest oxidation potential is reached at pH 9.4.
Meanwhile, Fig. 3 shows the diagram of thermodynamic stability Eh-pH
for the gold-glycine at temperature of 40 °C in 0.5 M of glycine. As may
be noted, the elemental gold is the species stable at all values of pH and
potential under 0.5 V; for higher values, there is a zone of stability for
the formation of the complex gold-glycine, although the lowest oxida-
tion potential is reached at pH 9.4. However, at higher values of po-
tential of 0.5 V and pH 11, the predominant species is Au(OH)2−, which
AuOH 2+
1.5 Au(OH) 2 +

Au(OH) 3 (c)
3. Thermodynamic analysis

The thermodynamic analysis was performed with the Hydra –

Medusa software suite, where the effect of the concentration of oxi- Au(OH) 4 −
1.0 Au(OH) 5 2 −
dizing agent and pH, to determine the potentially adequate conditions
Au(Gly) −
ESHE / V

and interpretations of the kinetics for gold leaching. The stability

constant for the complex gold-glycine complex was given by Aylmore
(2005) and the reagent concentrations to be evaluated by Eksteen and

Table 1 0.5 Au(OH) 2 −

Conditions of the computer pin leaching experiments.
Au(c)
Reagents Oxidizing agents (concentration) PH

Glutamate KMnO4 (0.03 M) 9.4

Glutamate H2O2 (0.03 M) 9.4
Glutamate KMnO4 (0.01 M) 11 0.0
Glutamate KMnO4 (0.04 M) 11 0 2 4 6 8 10 12 14
Glycine H2O2 (0.03 M) 9.4
Glycine KMnO4 (0.01 M) 11 pH
Glycine KMnO4 (0.04 M) 11
Fig. 2. Eh-pH diagram for the Au-glycine system at 25 °C, [Au] = 10−5 M, [Gly] = 0.5 M.

80
C.G. Perea, O.J. Restrepo Hydrometallurgy 177 (2018) 79–85

1.5 A u(O H ) 2+ 1.5

A uO H 2+
A u (O H ) 3 (c)

A u(O H ) 4− 1.0
A u(O H ) 52−
A u(G ly) − Cu 2+
1.0 Cu(Gly) +

/ V
Cu(Gly) 2 Cu(OH) 42−
ESHE / V

0.5

SH E
A u (O H ) 2 −

E
0.5
0.0
Au(c)

Cu(Gly) 2−
Cu(cr) Cu(OH) 2−

0.0 -0.5
0 2 4 6 8 10 12 14
0 2 4 6 8 10 12 14
pH Fig. 5. Eh-pH diagram for the Cu-glycine system at 25 °C, [Cu] = 10−5 M, [Gly] = 0.5 M.

Fig. 3. Eh-pH diagram for the Au-glycine system at 40 °C, [Au] = 10−5 M, [Gly] = 0.5 M.
waste, such as computer pins. For that reason, these were pretreated in
an oxidizing medium to remove the other metals, especially copper.
can generate a passivation that affects the leaching process.
Based on this analysis, the chosen testing conditions were pH 9.4
4. Results and discussion
and 11, which is within the range in which the oxidation reaction could
occur with 0.5 M glycine. On the other hand, at lower glycine con-
4.1. Characterization of the computer pins
centrations, the oxidation is more difficult, as may be observed in Fig. 4;
at 0.5 M (log10[Gly] = −0.3), the oxidation potential is approximately
The analysis of the pins employed in the leach testing was per-
0.5 V, while at 0.01 M, the potential is 150 mV higher. For that reason,
formed using Scanning Electron Microscopy (SEM), with EDX. The
0.5 M glycine was chosen for the leaching solution.
cross-section of the sample showed the existence of three layers in each
However, the most important disadvantage associated with the use
of the pins: a core composed mainly of Cu and with small amounts of Sn
of glycine is its great affinity for copper ions. At conditions, similar to
(Fig. 6), a coating in the central zone consisting of Al, Cu, Fe, and Ni
those used to leach gold (0.5 M glycine and pH 9.4 and 11), copper is
(Figs. 7 and 8), with an average thickness of 80 μm and finally, an outer
oxidized at potentials approximately 800 mV lower (Fig. 5). This im-
layer of a very thin gold film, with a thickness of less than 10 μm
plies that if metallic copper is present in the material to be leached, it
(Fig. 9).
will be preferentially dissolved, consuming oxidant as well as glycine.
The results of the semi-quantification in general reveal variation of
For that reason, any metallic copper should be removed from the solid,
the elements in the pins in terms of content and proportions. For ex-
before leaching gold. This may not be the case in refractory copper
ample, in the core, the Cu concentrations are at least 97% and the Sn
sulfide minerals, but is particularly important in the treatment of e-
less than 3%, in atomic percentage. The composition of the first coating
(which borders the core) varies: 6–41% Fe, 3–17% Ni, 13–34% Cu and
1.5 5–71% Al; gold is less than 4%. In the outer-most layer, the atomic
percentages of gold are 83–91%, while Cu varies between 4 and 9%, Ni
pH 9.4 is less than 7% and Al less than 3%.
Because the SEM results are non - quantitative and only show point
Au(OH) 3 (c)
values, they are not adequate to determine the gold composition of the
sample. For that reason, Regia digestions were performed on several
1.0 samples, which were subsequently analyzed by atomic absorption
spectrophotometry. A sizeable disparity in the gold and copper content
ESHE / V

is presented in Table 2. Because of this variability, a metallurgical

Au(Gly) −
balance (gold extracted + gold remaining in the residue) was calcu-
lated for each leaching experiment and results are reported as % ex-
traction.
0.5
4.2. Leaching test
Au(c)

4.2.1. Preparation of the material (pretreatment)

As was mentioned previously, thermodynamic predictions and the
0.0 results found by Eksteen and Oraby (2015a,b,c) show the great affinity
of copper for glycine. Consequently, pre-treatment of the pins with
-5 -4 -3 -2 -1 0 sulfuric acid and hydrogen peroxide performed to remove the copper
Log [Gly− ] TOT
present in these, since this element constitutes the largest percentage of
composition and so as not to affect the process of leaching of gold with
Fig. 4. Eh-log10 [glycine] diagram at pH 9.4 and 25 °C for the Au-glycine system, glycine and glutamate. As a result of the pretreatment, the weight of the
[Au] = 10−5 M.
final residue was only 20–25% that of the original sample.

81
C.G. Perea, O.J. Restrepo
Fig. 6. Electron micrograph SEM and EDX of the pin core.
Fig. 7. SEM micrograph of the average thickness of the core.
4.2.2. Leaching
Each leaching test employed 39 mg of the residue in 100 ml of the
corresponding solution. Listed below are some of the most effective
leaching tests, with their respective conditions and results:
Fig. 8. Electron micrograph SEM and EDX central zone (core coating).
82
Hydrometallurgy 177 (2018) 79–85
4.3. Effect of the oxidizing agent
To study the effect of the oxidizing agent in the leaching of gold in
solution of monosodium glutamate, is added hydrogen peroxide (H2O2)
and potassium permanganate (KMnO4) both to a concentration of
0.03 M to 0.5 M glutamate solution at room temperature (Fig. 10).
The results show that oxidizing with hydrogen peroxide is less ef-
fective in glutamate solution in comparison with KMnO4. This is due to
the fact that H2O2 favors the reaction of the amino acid with copper,
given that under these conditions high concentrations of copper were
obtained in solution, especially at the second hour, where the greatest
decrease in the percentage of gold extraction occurs (data not shown
here).
4.4. Effect of oxidizing agent concentration
The effect of the concentration of potassium permanganate on the
dissolution of gold in solutions of glycine and glutamate is shown in
Figs. 11 and 12, respectively. It is clear that by increasing the con-
centration of KMnO4, the extraction of gold increases slightly. In gen-
eral terms, the dissolution of gold depends on the concentration of
KMnO4, which would be limiting reagent in solutions of potassium
permanganate-glycine and glutamate‑potassium permanganate. How-
ever, excess oxidant has been shown to promote degradation of the
reagents affecting the extraction of gold.
In the results shown, low concentrations of potassium
C.G. Perea, O.J. Restrepo Hydrometallurgy 177 (2018) 79–85

Fig. 9. SEM and EDX electron micrograph of the pin surface (gold layer).

Table 2 2.50
Percentage of elemental composition of the pins.

Element Average Uncertainty 2.00

Au Extracon, %
(%) (+/−)
1.50
Au 0.64 0.24
0.01 M KMnO4
Fe 0.115 0.085 1.00
Cu 68.1 4.3 0.004 M KMnO4
Ni 6.365 5.735
Zn 0.005 0.005 0.50
Ag 0.05 0.05
Pb 0.245 0.245
0.00
0 10 20 30
14.00 Time (h)

12.00 Fig. 12. Effect of the concentration of oxidizing agent on the dissolution of gold:
[Glut] = 0.5 M, pH 11.
10.00
Au extracon, %

8.00 permanganate were employed in order to avoid reagent degradation. At

low concentrations, reaction rates are much lower and a stagnation of
6.00 KMNO4
the reaction occurs, although it presents a greater stability in the for-
H2O2 mation of the complex since there is no re-precipitation of gold in so-
4.00
lution. This phenomenon of stagnation can be due to the fact that under
2.00 these conditions of pH and low values of potential the predominant
species would be (AuOH) auroso hydroxide and its presence might
0.00 generate passivation of the gold surface, preventing the reaction with
0 5 10 15 20 25 30
amino acids.
Time (h)

Fig. 10. Effect of oxidizing agent on the dissolution of gold: [Glut] = 0.5 M, [H2O2] and 4.5. Effect of solvent type
[KMnO4] = 0.03 M, pH 9.44.

In Fig. 13, the reaction of both amino acids with the gold is possible,
4.50 achieving a greater extraction in the case of glycine. There is re-pre-
4.00 cipitation of gold with both ligands after 2 h and with glycine after 20 h.
3.50 The oxidizing agent favors the reaction of both amino acids with
copper, given that in these conditions high concentrations of copper in
Au Extracon, %

3.00
solution were obtained. According to Eksteen and Oraby (2015a,b,c),
2.50 0.01 M KMnO4 the evaluation the gold dissolution with these amino acids should be
2.00 0.004 M KMnO4 only after 150 h.
1.50 In Fig. 14 is used in low concentrations of potassium permanganate,
1.00 showing a slightly greater extraction with glycine, but are observed
0.50 reaction rates much lower and a slight stagnation of the reaction, al-
0.00 though it presents a greater stability in the formation of the complex as
0 5 10 15 20 25 30 it is not re-precipitation of gold in solution. In the end, however, the
Time (h) degradation of both reagents due to the oxidizing agent is very strong.
Fig. 11. Effect of the concentration of oxidizing agent on the dissolution of gold:
[Gly] = 0.5 M, pH 11. 4.6. Effect of copper ions

To study the behavior of the gold in the absence and presence of

83
C.G. Perea, O.J. Restrepo Hydrometallurgy 177 (2018) 79–85

3.50 0.80
0.70
3.00
0.60
2.50 with copper ions

Au extracon, %
Au Extracon, %

0.50
2.00 without copper ions
Glycine 0.40
1.50 Glutamate 0.30
1.00 0.20

0.50 0.10
0.00
0.00
0 5 10 15 20 25 30
0 5 10 15 20 25 30
Time (h)
Time (h)
Fig. 16. Percentage of extraction of gold in the [Gly] = 0.5 M, [Cu2+/Cu+] = 50 ppm at
Fig. 13. Effect of the type of solvent on the dissolution of gold: [Gly] = 0.5 M, pH = 10.1 and [KMnO4] = 0.01 M.
[Glut] = 0.5 M, [H2O2] = 0.03 M, pH 9.44.

0.7
5
0.6
4
0.5

Au Extracon, %
Au Extracon, %

3 0.4

Glycine 0.3 25°C

2
Glutamate 40°C
0.2
1
0.1

0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time (h) Time (h)

Fig. 14. Effect of the type of solvent on the dissolution of gold: [Gly] = 0.5 M, Fig. 17. Effect of temperature on the rate of extraction of gold, [Gly] = 0.5 M,
[Glut] = 0.5 M, [KMnO4] = 0.01 M, pH 11. [KMnO4] = 0.01 M, pH = 11.

1.80 4.7. Effect of temperature

1.60
Eksteen and Oraby (2015a,b,c) evaluated the effect of temperature
1.40
on the kinetics of dissolution of gold in a 0.1 M glycine solution with
Au ExtracƟon, %

1.20 hydrogen peroxide at temperatures of 23, 30, 40, 60 and 75 °C. They
1.00 found that the dissolution of gold increases with temperature. This re-
with copper ions sult was verified by a test comparing the leaching behavior of gold foil
0.80
without copper ions with potassium permanganate to 0.004 M and 0.5 M glycine with
0.60
pH 11, at 25 °C and 40 °C (Fig. 17).
0.40
0.20 5. Conclusions
0.00
0 5 10 15 20 25 30 It has been shown that the type of oxidizing agent and its con-
Time (h) centration affect gold leaching kinetics. The highest percentage of ex-
traction was achieved with glutamate using 0.03 M potassium per-
Fig. 15. Percentage of extraction of gold in the [Glut] = 0.5 M, [Cu2+/Cu+] = 100 ppm
manganate as an oxidant at pH 9.4. The addition of Cu2+ systems,
at pH = 11 and [KMnO4] = 0.01 M.
together with potassium permanganate, using either glycine or gluta-
mate improves the gold extraction.
added copper ions, additional two leaching test were performed using The great affinity between the amino acids and copper negatively
5 mg of gold samples with 99.95% purity in selected conditions, based affects the process of gold leaching. The present study showed gold
on the thermodynamic analysis, the above results and a review of the leaching with these reagents has very slow kinetics in comparison with
literature. In Figs. 15 and 16 it can be noted that the percentage of gold that of cyanide, which renders their application inconvenient, as re-
extraction in a solution of glycine with copper ions (Cu2+/Cu+) is agents for agitated leach systems in the gold industry.
greater than that obtained without the added copper ions; after 24 h, In the glycine‑potassium permanganate system, the kinetics of
the extraction is doubled. Similar behavior may be observed in gluta- leaching is strongly affected by the temperature, which indicates that
mate solutions, achieving 6 times the extraction with copper ions in the reaction mechanism is chemically controlled.
24 h. This indicates that possibly the copper ions avoids the passivation
of the gold. References

Avraamides, J., 1982. Prospects for alternative leaching systems for gold: a review. In:
Carbon-in-Pulp Seminar. The Aus.I.M.M. Perth and kaigooriie branches and murdoch

84
C.G. Perea, O.J. Restrepo
university.
Aylmore, M., 2005. Alternative lixiviants to cyanide for leaching gold ores. Dev. Min.
Process. 501–539.
Eksteen, J., Oraby, E., 2015a. Gold leaching in cyanide-starved copper solutions in the
presence of glycine. Hydrometallurgy 81–88.
Eksteen, J., Oraby, E., 2015b. The leaching and adsorption of gold using low con-
centration amino acids and hydrogen peroxide: effect of catalytic ions, sulphide
minerals and amino acid type. Miner. Eng. 36–42.
Eksteen, J., Oraby, E., 2015c. The leaching of gold, silver and their alloys in alkaline
glycine-peroxide solutions and their adsorption on coal. Hydrometallurgy 199–203.
Galindo, L., 2013. Alternative Methods to the Cyanide Leaching of Precious Metals.
85
Hydrometallurgy 177 (2018) 79–85
National University of Colombia, Medellín, Antioquia, Colombia.
Guzmán, E., 2013. Gold Using Multiple Paths from a Metallurgical Material Concentrated
in the Municipality of Abejorral, Antioquia. National University of Colombia,
Medellín, Antioquia, Colombia.
Oraby, E., Eksteen, J., 2014. The selective leaching of copper from a gold–copper con-
centrate in glycine solutions. Hydrometallurgy 14–19.
Poisot, M., 2010. Study of Factors Affecting the Process of Electrodeposito Gold and Silver
from Solutions of Thiourea in a Reactor Type Filter Press. Federal Distro of the
Iztapalapa, Mexico. Cambridge University Press.
The corral, G., 2003. Assessment of the Role and the Potential of the Mining Foundations
and their Interaction with Local Communities. ECLAC, Santiago de Chile.