Hydrometallurgy 185 (2019) 186–193

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

Microfluidic study of sustainable gold leaching using glycine solution T

⁎
M.R. Azadi, A. Karrech , M. Elchalakani, M. Attar
Department of Civil, Environmental and Mining Engineering, University of Western Australia, 35 Stirling Hwy, Crawley, WA 6009, Australia

A R T I C LE I N FO A B S T R A C T

Keywords: The purpose of this paper is to investigate the in-situ leaching of gold using a microfluidic system with controlled
Microchannel system flow, temperature and fluid composition. The microfluidic system is a microchannel embedding a nano-scale
Glycine layer of gold over which the fluid can flow and etch (erode) gold at various temperatures and concentrations of
Leaching lixiviant. The lixiviant in this case is an alkaline glycine system that has been identified as an environmentally
Gold
friendly substance to dissolve precious metals, it is used to extract gold within the engineered micro-cavity. As
the fluid flows in the microchannel, the thickness of the gold layer is monitored to control its reduction with
respect to time and space. The experimental conditions were varied to evaluate their effects on the recovery rate.
The results show that compared to traditional methods being used in laboratory testing, this technique can
provide real time measurements with low consumption of chemicals and the results can be obtained in shorter
periods of time.

1. Introduction geological setting. However, a microchannel is an appropriate means to

Microelectronics technology has been developing over > 60 years
and has produced valuable devices for a broad range of applications
(Moore, 1965; Manz et al., 1990; Henry et al., 2000; Becker and
Locascio, 2002; Temiz et al., 2015). In particular, microfluidic systems
have been instrumental in biochemistry and microbiology and have
helped characterising the chemical and physical mechanisms that occur
at the micro-scale (Melin and Quake, 2007; Yeo et al., 2011; Sackmann
et al., 2014; Halldorsson et al., 2015). As they can be used to manip-
ulate small amounts of fluids in micro-scale channels (Whitesides,
2006), microfluidic systems have been used to extract some metals such
as Ag (Nagai et al., 2009), Cu/Cr (Priest et al., 2011, 2012, 2013), Co
(Minagawa et al., 2001), Pt (Kriel et al., 2015), Pd (Yin et al., 2013),
and rare earth elements (Kolar et al., 2016; Chen et al., 2017).
In recent years, in-situ leaching has emerged as a viable solution to
extract various commodities including precious metals and started at-
tracting a renewed interest Karrech et al. (2018). Understanding the
process of in-situ leaching requires advanced tools of thermal-hy-
draulic-mechanical-chemical coupling within the principles of non-
equilibrium thermodynamics (Poulet et al., 2010, 2012; Karrech et al.,
2012; Karrech, 2013; Karrech et al., 2015) and mineralisation (Zhang
et al., 2012, 2013). Such formulations require accurate description of
leaching locally at the pore scale. To avoid ambiguity, it is important to
note that the microfluidic system used in this paper is not to simulate
the injection and extraction process per se as it happens in large scale
mimic the process within a single pore space of an established local
fracture in a deposit.
In hydrometallurgy, leaching is the main stage of mineral processing
and often has significant effects on subsequent steps (Crundwell, 2011,
2013). Many studies have been conducted on metal dissolution in order
to understand the behaviour of leachates and lixiviants, identify the
kinetic parameters, and optimize the overall efficiency of hydro-
metallurgical operations (Crundwell, 2013). Recently, Kotova et al.
(2017) conducted a pioneering experimental study on gold leaching by
amonium thiosulfate using microchannels and monitored the etching
rate of gold in real time under controlled conditions. In comparison
with traditional leaching experiments, this new technique offers a vi-
sual and quantitative monitoring in a confined space under controlled
laminar flow rates. Kotova et al. (2017) conducted their experiment
using a high aspect ratio microchannel to mimic a crack in a miner-
alised sample. Yang and Priest (2018) introduced a microfluidic device
to study thiosulfate leaching of gold by adding temperature screening to
determine the activation energy. Their results show the difficulty of
leaching above 270 °C due to possible diffusion of chromium adhesion
between the gold film and substrate. They reveal that the leaching rate
is affected by the stoichiometric ratio of thiosulfate, ammonia, and
copper in the solution. In the current paper, we upgrade the design by
including a temperature controlled system and we use alkaline glycine
solutions instead of amonium thiosulfate. The flow rate can vary based
on the joint aperture and the flow is assumed to be analogous and

⁎
Corresponding author.
E-mail address: ali.karrech@uwa.edu.au (A. Karrech).

https://doi.org/10.1016/j.hydromet.2019.02.009
Received 18 September 2018; Received in revised form 20 December 2018; Accepted 15 February 2019
Available online 25 February 2019
0304-386X/ © 2019 Elsevier B.V. All rights reserved.
M.R. Azadi, et al. Hydrometallurgy 185 (2019) 186–193

Fig. 2. Experimental set-up: alkaline glycine solution injected through a mi-

crochannel to leach gold. The thickness of the gold layer is monitored by a
camera from the top while a white back LED backlight is used to illuminate the
device.

Fig. 1. Schematic process of microchannel parapration steps. Oxygen plasma

machine was used to etch the PMMA substrate to make the channel. Photoresist
was used to protect the surface of PMMA rather than the channel area. Au
Fig. 3. Calibration curve of gold thickness versus luminosity.
(60 nm) was caoted on the channel using thermal evaporation techniques. The
UV glue was applied to bond two substrates.
pH and temperature.
Table 1
The list of lixiviant samples used in the experiment at different temperature, 2. Materials and methods
pH, glycine and H2O2 concentrations.
2.1. Microchannel preparation
Lixiviant no. Glycine (M) H2O2 (%) pH Temperature Flow rate
( ± 2 °C) (ml/h)
The microchannel preparation has been conducted at the Western
Sample 1 1.0 0.56 11 60 7.0 Australian Centre for Semiconductor Optoelectronics and Microsystems
Sample 2 1.5 0.56 11 60 7.0
(WACSOM) at The University of Western Australia. The WACSOM
Sample 3 1.0 0.56 12 60 7.0
Sample 4 0.5 0.56 10 60 7.0 fabrication facility is a cleanroom environment that has a low level of
Sample 5 1.0 0.56 9 60 7.0 environmental pollutants such as dust, airborne microbes, aerosol
Sample 6 1.0 0.40 12 75 7.0 particles and chemical vapors. In this study, we used a transparent and
Sample 7 1.2 0.40 12 75 7.0 colourless poly(methyl-methacrylate)(PMMA) material to make the
Sample 8 0.1 0.40 12 75 7.0
Sample 9 0.5 0.40 12 75 7.0
substrate/chip. A groove was included in the chip to represent the
Sample 10 0.5 0.40 12 70 7.0 microchannel and PMMA cover sheets were used to confine the flow.
The PMMA sheets-purchased from Goodfellow (UK)-were cut to fit the
chip size (150 × 150 × 2 mm). The nominal working temperature of
laminar between two highly smooth parallel plates. However, as real this PMMA is between 50 and 90 °C, which is within the range of
surfaces are not necessarily smooth or parallel enough and they con- temperatures covered in this experiment. The PMMA has good abrasion
verge abruptly at their ends, turbulent flow may also occur (Gangi, and UV resistance and excellent optical clarity. It is inert to the che-
1978; Brown and Scholz, 1985). In this work, flow is laminar within the micals used in this study and to the heat applied in the preparation
ranges of the velocity of fluid through the micro-channel, size of the process. PMMA characteristics have been examined and discussed in
aperture and physical properties of water-glycine. We present a visual numerous studies (Henry et al., 1999; Henry, 2001; Aquino, 2005;
and quantitative analysis of gold leaching by alkaline glycine in con- Mathur et al., 2009; Prakash and Kumar, 2015). Inlet and outlet holes
fined and high aspect ratio channels under controlled fluid flow rates, (1.6 mm) were drilled in the chip to circulate the fluid. The distance

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M.R. Azadi, et al. Hydrometallurgy 185 (2019) 186–193

microchannel were checked by profilometer Dektak 150 and high re-

solution microscope ZYGO 6300.

2.2. Choice of lixiviant

In recent years, there has been an increasing interest in studying in-

situ leaching (ISL) of gold using non-cyianidation system such as iodine
(Karrech et al., 2018; Martens et al., 2012; Wu et al., 2012). Finding
more environmently friendy chemicals as a replacement for cyanide can
make ISL more viable. A considerable number of studies have been
conducted on the amino acids (including glycine) and metals reactions
(Monk, 1951; Martin et al., 1971; Farooq and Ahmad, 1974; Kiss et al.,
1991; Mironov, 2007; Isaeva et al., 2008; Angkawijaya et al., 2012).
The effect of pH and temperature on the solubility of gold in amino
acids has been examined by Jingrong et al. (1996). It has been shown
that the presence of hydrogen peroxide can enhancethe solubility of
gold in amino acids (Brown et al., 1982). The effect of adding amino
acids to thiosulphate for leaching gold has been evaluated by Feng and
Van Deventer (2011). These authors found that gold recovery increases
as amino acids are added to thiosulphate solutions. The following
equations have been suggested by Aylmore (2005) as an example of
gold dissolution reactions where the amino acid glycine is a ligand:
Fig. 4. Images of gold layers captured after 0, 20 and 40 mins of the leaching.
4Au + 8NH2 CH2 COOH + 4NaOH + O2 = 4Na[Au(NH2CH2COO)2]
The points A, B and C show the distance from the injection point. The fluid is
injected from left to right with a flow rate 7 ml/h: 1 M glycine, 0.4% H2O2, + 6H2 O (1)
pH 12, 75 ± 2 °C.
2Au + 4NH2CH2 COOH + 2NaOH + H2 O2 = 2Na[Au(NH2 CH2 COO)2]
between two holes has been adjusted with respect to the channel size + 4H2 O (2)
(4 mm × 40 mm). To avoid scratching the surface after removing the
Recently, experimental studies have been carried out to investigate
plastic cover, a small tong was used to carry the substrate all the time.
the application of glycine as an eco-friendly lixiviant for gold leaching
The substrate was washed with running water, dried by air and checked
in alkaline environment with the exposure to hydrogen peroxide (Oraby
under microscope for any dirts. Fig. 1 shows a schematic representation
and Eksteen, 2015; Eksteen et al., 2017). The experimental data suggest
of the microchannel preparation process. For the first step of fabrica-
that glycine is more effective at pH between 10 and 11 and temperature
tion, the substrate needed to be covered by photoresist to avoid etching
of 60 °C.
outside the channel area. For this purpose, the photoresist AZ 4562 was
In this study, we evaluate the leaching of gold using alkaline-gly-
selected. The substrate was placed in a spinning machine, covered with
cine. For this purpose, deionized (DI) water and glycine (ReagentPlus,
photoresist and allowed to spin for about 40 s at an angular speed of
≥99% HPLC) were used to prepare the solutions. Sodium hydroxide
2000 rpm. The substrate was then placed on a hot plate (90 °C) for 120 s
has been used to adjust the pH and hydrogen peroxide has been added
to bake the layer of photoresist (8.8 μm). Using a mask, only the
to the solution right before exposure with gold. All chemicals have been
channel area was exposed to UV light for 1 min and washed up with the
purchased from Sigma-Altrich. In this experiment, nine different spe-
developer AZ 340. The substrate was then scanned under the micro-
cimens of aqueous glycine (see Table 1) have been examined to eval-
scope to make sure no photoresist was left in the channel area. To built
uate the effect of pH, temperature, and glycine concentration on the
a channel on the substrate, we used an oxygen plasma machine
leaching process. All sample were prepared using a beaker with a
(Plasma100) and a practical recipe (60% O2 and 5% CF4) to etch the
magnetic stirrer on a hot plate. The stirring process lasted for at least
surface of the PMMA substrate (12 μm). Thermal evaporation was used
1 h until a clear solution was obtained. Temperature and pH were
to deposit a layer of 5 nm Cr (for adherence between substrate and
regularly checked until stable conditions were reached.
gold) and a layer of 60 nm of gold on the channel. Thermal evaporation
is a the physical vapor deposition (PVD) technique in which the metal is
2.3. Experiment set-up
heated in a vacuum chamber until its surface atoms have sufficient
energy to leave the surface. At this point they will traverse the vacuum
Fig. 2 is a schematic representation of the experiment in which the
chamber, at thermal energy (< 1 eV), and coat on the substrate posi-
aqueous glycine is injected at a rate of 7 ml/h through the microchannel
tioned above the chamber.
(4 mm × 50 mm × 12 μm) to leach gold from the 60 nm gold layer
The rest of photoresist then was cleaned up from the substrate with
coated in the channel. To keep the temperature constant over the ex-
the developer AZ 340. The final step was boding two PMMA substrates
periment duration, a heating pad was used and temperature was con-
together. There are many different methods to bond two PMMA sub-
trolled by an infrared thermometer during the experiment. A white LED
strates including thermal bonding, chemical bonding using acetone/
backlight was used to illuminate the device and the thickness of the
ethanol, oxygen plasma activation, pressure bonding and UV assisted
gold layer was monitored using a microscope camera (Digitech) that
bonding (Leonard et al., 1985; Lei et al., 2004; Hsu and Chen, 2007;
captures the etching process in real time. Video files were recorded
Harris et al., 2010; Kim et al., 2010; Tran et al., 2013; Yu et al., 2015;
using the MicroCapture software through a 4 mm × 30 mm window.
Wan et al., 2017). Among the above methods, we used UV assisted glue
because it was easy to apply manually. In this method, a small amount
of the glue was applied on the surface and carefully spread on the 2.4. Method of analysis
substrate while care was taken to keep the channel clean of glue. In the
next step, two substrates were bonded by applying a load of 1 kg while The thickness of gold layer was monitored by a camera recording
curing by UV exposure. The thickness of the gold layer and the depth of video files from the top of microchannel. The video files were analyzed
using video Tracker 5.0.5 in which the brightness (luma) of a point can

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M.R. Azadi, et al.
Fig. 5. Gold thickness versus time at different conditions of temperature and glycine concentration. The points A, B and C shows the distance from the injection point
through the microchannel, respectively.
be tracked over a period of time. Samples with known gold layers
thicknesses were prepared and used to calibrate the thickness-lumin-
osity relationship as shown in Fig. 3. A thickness of 60 nm was selected
because it represents the opacity threshold as suggested by Kotova et al.
(2017).
Image analysis was conducted on the three different points, A, B and
C shown in Fig. 4 to see if the distance from the injection point has an
effect on the leaching process. Additional images were processed to
analyse the whole area of the micorchannel and examine the fingering
patterns that are produced according to the fluid flow pathways.
3. Results and discussions
The experiment was conducted with 10 samples (see Table 1) to
check the effect of temperature, pH and glycine concentration on gold
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Hydrometallurgy 185 (2019) 186–193
leaching. Fig. 5 shows the experimental results that were obtained
under different leaching conditions. Samples 4, 5 and 8 were less af-
fected after 12 h (no changes were observed on the gold thickness to be
analyzed). Samples 6 and 7 had the most significant effects on the
leaching process; the gold layer thicknesses decreased to zero after 30
mins. In the cases of samples 1, 3 and 9 the gold layer thicknesses re-
duced to zero after 12 h. As can be seen in Fig. 5, the leaching process
was more effective at point A that is spatially closer to the injection
point. This could be attributed to the decrease of flow velocity due to
friction near the gold surface and towards the end of the channel. Since
the regime of the flow is laminar (the channel is of small size), the speed
profile in the confined channel is parabolic and the flow speed is
maximum in the middle and minimum at the boundaries. Sample 2 also
shows a low leaching rate, although glycine concentration is as high as
1.5 M. This may be explained by the passivated layers of gold
M.R. Azadi, et al. Hydrometallurgy 185 (2019) 186–193

dissolution and/or polymerization of glycine which increases the visc-

osity of solution. Fig. 6a shows the white particles appeared as dark
stains on the channel. Fig. 6b shows a microscopic (40×) images of
possible polymerization of glycine extracted from the pregnant solution
in sample 2.

3.1. Effect of pH

Glycine complexes variably with metals as a function of pH (Kiss

et al., 1991). In aqueous solutions containing amino acids such as
glycine, increasing the pH increases the solubility of gold (Brown et al.,
1982; Jingrong et al., 1996; Oraby and Eksteen, 2015). By comparing
the results in samples 1, 3 and 5, it can be seen from Fig. 6 that in-
creasing pH increases the leaching rate. Fig. 7 shows the graph of gold
thickness versus time; the gold layer thickness decreases in less time as
pH increases. It can be seen that pH beyond 11 can be more effective for
alkaline glycine lixiviant.

3.2. Effect of temperature

Fig. 6. (a) White particles in the microchannel in sample 2. (b) Possible poly-
merization of glycine within the pregnant solution. As can be seen from Fig. 5, sample 6 and 7 show dramatic increases
in the rate of gold dissolution at pH 12 and temperature 75 ± 2 °C.
Some experimental studies on the solubility of gold in amino acid so-
lutions at different temperatures have been conducted by Jingrong et al.
(1996), which have shown the maximum solubility of gold is produced
at 80 °C. The effect of temperature on gold leaching in alkaline glycine
solutions have been experimentally studied by Oraby and Eksteen
(2015) who conducted beaker-scale experiments over periods of time
up to 48 h. Their results indicate that the gold dissolution increases
dramatically as temperature increases. Comparing sample 3 and sample
9 (see Fig. 5), it can be seen that the recovery rates are close although
the temperatures are from 60 to 75 °C, respectively while the glycine
concentrations are 1 M and 0.5 M, respectively. Fig. 8 obtained by
comparing the outputs of Samples 3, 6 and 10 shows a dramatical in-
crease of gold recovery by increasing temperature from 60 ± 2 to
75 ± 2 °C. Following Darcy's law, the flow rate is inversely propor-
tional to the viscosity of the liquid. As an example, it has been de-
monstrated that percolation rate into particles of aqueous leaching so-
lution can be 5 times higher at at 80 °C than at 5 °C (Julian and Smart,
1907; Vizsolyi et al., 1963). It should be mentioned that although the
injection rate is fixed at 7 ml/h, the flow rate may be affected by
Fig. 7. Effect of pH on gold dissolution in samples 1, 3 and 5. It shows that
temperature and temporary evaporation.
increasing pH increases the rate of gold dissolution as the thickness of gold
layer is reduced.
3.3. Effect of glycine concentration

Our experimental results indicate that increasing the concentration

of glycine increases the gold dissolution rate, provided that the con-
centration remains below the polymerization level that depends on
temperature and pH (Sakata et al., 2010). Excessively high glycine
concentrations may result in adverse effects because if glycine poly-
merises, it hinders the flow. In addition, surface passivation may reduce
the rate of etching/leaching (Fairley, 1998; Feng and Van Deventer,
2010; Kotova et al., 2017). Note that the solubility of glycine in water
can be increased by increasing temperature Budavari et al. (1996).
Fig. 9 shows that increasing the glycine concentration up to 1.2 M in-
creases the gold dissolution in samples 6, 7, 8 and 9 at 75 °C (Table 1).
However, Fig. 10 shows that increasing the glycine concentration from
1 to 1.5 M (in samples 1 and 2, respectively) reduces the rate of gold
dissolution. As mentioned before, high concentration of glycine may
cause passivation of the gold surface which can reduce the dissolution
rate.

4. Monitoring gold leaching throughout the channel

Fig. 8. Effect of temperature on gold dissolution in samples 3 and 6.
In the previous sections, we show that the microchannel system is
instrumental to evaluate the effects of temperature, pH and glycine

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M.R. Azadi, et al.
Fig. 9. Effect of glycine concentration on gold dissolution in samples 6, 7, 8 and
9. Increasing glycine concentration at temperature 75 ± 2 °C increases the rate
of gold dissolution.
Fig. 10. Effect of glycine concentration on gold dissolution in samples 1 and 2.
Inceasing the glycine concentration at temperature 60 ± °C from 1 to 1.5 M
decreases the rate of gold dissolution.
Fig. 11. Etch profile of Au thickness versus time in sample 6 at points A, B and C as shown in Fig. 4.
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Hydrometallurgy 185 (2019) 186–193
Fig. 12. Contour plots of Au thickness across the microchannel at intervals of
5 min in sample 6.
concentration on gold leaching within a confined space that mimics
micro-cracks. One of the main advantages of using the michrochannel is
the ability to monitor leaching rates during the experiment and the
possibility to observe the finger-like pattern that characterise the
etching process in real time. Fig. 11 shows the three etch profiles across
the microchannel in sample 6. As can be seen, the leaching rate is fully
monitored with respect to space and time within the microchannel. The
figure also shows that the leaching rate reduces close to the walls be-
cause the lowest flow velocity occurs in these areas. The leaching rate
M.R. Azadi, et al.
also decreases from profiles A to C (see Fig. 4) because of the distance
from injection point.
To evaluate the effects of friction on the velocity of flow and con-
sequently on the leaching rate, more profile lines were drawn across the
channel for sample 6. By combining the profile lines and measuring the
gold thickness at 300 points within the microchannel surface, contour
plots of gold thickness were obtained at intervals of 5 min (Fig. 12). It
can be seen in Fig. 12 that leaching started in the left area close to the
injection points and moved towards the right side. In addition, the re-
sults show that leaching intensified in the middle of the microchannel
and decreased at the areas close to the lateral sides. Video Tracker 5.0.5
and Surfer® 16 from Golden Software, LLC (www.goldensoftware.com)
were employed to obtain the gold thickness across the channel and the
contour graphs.
Compared to other laboratory tests, this method mimics the in-situ
gold etching process in micro-cavities. Yet, the system has certain
limitations and can be improved in the future. For example selecting the
right material to make the substrates and covering sheets can be critical
as some materials can be opaque to the light, react with the lixiviants or
sensitive to temperature. Controlling the temperature within a small
range throughout the channel can be difficult with the current tech-
nology where a single thermocouple is used to measure temperature. In
addition, preparing proper microchannels is challenging, expensive,
and dependent on the type of metal or elements to be leached.
5. Conclusion
A microfluidic device has been developed to mimic the conditions of
in-situ leaching of gold using an alkaline glycine system at various
temperatures and lixiviant concentrations. The device builds on an
existing device developed by Kotova et al. (2017) where amonium
thiosulfate has been used to extract gold at room temperature. The
device was instrumental to conduct the experiment and quantitatively
monitor the leaching process under controlled conditions at full scale. It
has been shown that increasing temperature around 75 °C dramatically
increases the leaching rate of gold in alkaline glycine solutions. It has
also been noticed that increasing pH to 11 and beyond can increase the
leaching rate. Although increasing glycine concentration improves the
rate of leaching to some extend, excessively high concentrations of
glycine can reduce the recovery. This study shows that microchannel
systems have a great potential for future mining and metallurgy studies
where in-situ leaching under controlled conditions is relevant.
Acknowledgements
This project was supported by the Australian Research Council
through the Discovery Project DP170104205. This support is highly
appreciated. M.R. Azadi would like to acknowledge the financial sup-
port provided by Robert and Maude Gledden Postgraduate
Scholarships. In addition, the authors thank Dr. Mariusz Martyniuk, Dr.
Adrian Keating, Dr. Dhirendra Tripathi, Dr. Xiao Sun, Dr. Hemendra
Kala and Dr. Martin Hill for valuable advices and great assistance in
making the microchannels.
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