Minerals Engineering 191 (2023) 107979

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Evaluation of acid mine drainage (AMD) from tailings and their

valorization by copper recovery
A. Ruiz-Sánchez a, b, *, Julio C. Juárez Tapia a, G.T. Lapidus c
a
Área Académica de Ciencias de la Tierra y Materiales, Universidad Autónoma del Estado de Hidalgo (UAEH), Pachuca de Soto, Hidalgo C.P 42184, Mexico
b
Tecnológico Nacional de México, Instituto Tecnológico de Boca del Río, México, Carretera Veracruz-Cordoba Km 12, C.P 94290 Boca del Río, Ver, Mexico
c
Universidad Autónoma Metropolitana Unidad Iztapalapa, Departamento de Ingeniería de Procesos e Hidráulica, Universidad Autónoma Metropolitana-Iztapalapa, San
Rafael Atlixco No. 186, Colonia Leyes de Reforma 1a sección Alcaldía de Iztapalapa, Ciudad de México 09310 Mexico

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

Keywords: Recent investigations have found that the mining industry generates approximately 10 billion tons of tailings per
Mine tailings year, tending towards doubling this amount by 2035. For this reason, a systematic method is needed to study acid
Acid mine drainage mine drainage (AMD) potential, as well as determining the dissolution of potentially toxic elements (PTEs).
Copper recovery
Furthermore, the possible recovery of base or precious metals could transform the tailings into value-added
Solvent extraction
materials. In the present investigation, the potential for the generation of acid mine drainage in a sample of
mine tailings was evaluated, as well as an analysis of the dissolution of PTEs through a sequential extraction of
appropriate chemical solutions with increasing strength of reactivity to identify base or precious metals that can
be recovered through a metallurgical process consisting of leaching, solvent extraction and electrolysis, operating
at moderate pressure and temperature. The results of this research showed that these tailings contain approxi­
mately 3.7% of pyrite occluded in silicates and therefore are not a high risk for generating acid drainage and
PTEs dissolution. On the other hand, a process for obtaining metallic copper was proposed, which resulted in a
leaching liquor with 1226 ppm using 0.21 M H2SO4 and a pulp density of 300 g/L. Solvent extraction in a single
stage allowed the leach liquor to be concentrated at 9200 mg Cu/L, recovering the majority of the copper in
metallic form by electrolysis.

1. Introduction
Mining is one of the main activities that has contributed to the
economic development of Mexico. However, this activity is responsible
for the generation of waste, such as mine water, rock waste and mine
tailings. Rock residues correspond to the amount of soil removed in the
deposits prior to the exploitation of the minerals of interest, as well as
those solid residues obtained after concentrating the minerals of value
by physical and chemical methods (Nwaila et al., 2021a; b). On the other
hand, mine tailings correspond to those solid residues resulting from the
processing of minerals once the values of commercial interest such as
Cu, Pb, Zn, Ag and Au have been recovered by metallurgical means.
According to Araya et al. (2020, 2021) worldwide, the mining industry
generates around 10 billion tons of tailings per year, with the tendency
for this amount to double by the year 2035.
The main problem associated with mine tailings is the generation of
AMD due to the oxidation of sulfide-type minerals present in this type of
waste. The oxidation of sulfides is promoted at the deposit site mainly by
microbial activity (Thiobacillus ferrooxidans), moisture and oxygen
(Nwaila et al., 2021a; b).
The acid generated (H+) in the oxidation of sulfide-type minerals can
give rise to the dissolution of other mineralogical phases that contain
PTEs, such as Cr, Pb, Ni, Cu, Zn, As, Cd, Fe, Al, Se, Te, Mo and Hg, which
affect the abiotic environment (water and soil, mainly aquifers) and the
health of living organisms (human beings and animals) that inhabit the
limits of the deposit of this kind waste. Fortunately, the generated acid
can be neutralized naturally by the silicates, hydroxides and carbonates
(known as acid buffers) present in the mine tailings (Remon et al., 2005;
Hernández-Mendiola et al., 2016; Gómez-Bernal et al., 2017; Salas-
Luévano et al., 2017; Flores de la Torre et al., 2018; Armienta et al.,
2016).
In Mexico, the mine tailings originated in the 450 years of mining

* Corresponding author at: Tecnológico Nacional de México, Instituto Tecnológico de Boca del Río, México, Carretera Veracruz-Cordoba Km 12, C.P 94290 Boca
del Río, Ver, Mexico
E-mail address: sanchez.angel@hotmail.com (A. Ruiz-Sánchez).

https://doi.org/10.1016/j.mineng.2022.107979
Received 31 July 2022; Received in revised form 2 December 2022; Accepted 10 December 2022
Available online 21 December 2022
0892-6875/© 2022 Elsevier Ltd. All rights reserved.
A. Ruiz-Sánchez et al.
activity carried out in over 50% of its territory; these are the product of
mainly amalgamation and cyanidation processes, used for gold and sil­
ver recovery. This has led to the accumulation of millions of tons of
tailings deposited in open-air tailings dams. In some cases, the mine
tailings located in northern Mexico have abundant vegetation on their
surface, which could indicate high chemical stability and no risk to the
environment; however, several studies have found high metal concen­
trations (Ramos-Arroyo and Siebe-Grabach,2006; Gómez-Bernal et al.,
2017).
As mentioned above, the generation of acid occurs by the oxidation
of sulfides (pyrite, pyrrhotite, covellite, chalcopyrite, enargite, etc.);
however, the abundant presence of pyrite is the reason this mineral
phase is generally considered in the representation of chemical reactions
of this process. Accordingly, reaction (1) corresponds to the oxidation of
pyrite due to oxygen and moisture, while reaction (2) suggests the im­
mediate oxidation of the ferrous ion by oxygen itself. If the pH estab­
lished at the deposition site is greater than 2, then a fraction of the ferric
ion produced in reaction (2) precipitates, giving rise to the generation of
3 mol of H+ (reaction (3)). Therefore, the overall process (reaction (4))
of pyrite oxidation generates 4 mol of H+.
7 1981; Dold, 2003; Hall et al.,1996). The method consists of placing the
FeS2 + O2 + H2 O→Fe2+ + 2SO4 2− + 2H+ (1)
2
1 1
Fe2+ + O2 + H+ →Fe3+ + H2 O (2)
4 2
Fe3+ + 3H2 O→Fe(OH)3 (s) + 3H+ (3)
FeS2 +
15 7
O2 + H2 O→Fe(OH)3 (s) + 2SO4 2− + 4H+ (4)
4 2
A comparison with the global processes for the oxidation of pyrite,
arsenopyrite and chalcopyrite shows that the oxidation of pyrite gen­
erates a greater number of moles of acid (reactions (5) and (6)).
Furthermore, under conditions of elevated acidity (pH < 2), the ferric
ion obtained in reaction (2), could act as an oxidizing agent, enhancing
the additional production of 16 mol of H+ (reaction (7)) in the oxidation
of pyrite.
7
FeAsS + O2 + 4H2 O→Fe(OH)3 (s) + SO4 2− + H2 AsO4 − + 3H+ (5)
2
17 5 could approximate the chemical conditions necessary to establish a
CuFeS2 + O2 + H2 O→Cu2+ + Fe(OH)3 (s) + 2SO4 2− + 2H+ (6)
4 2
FeS2 + 14Fe3+ + 8H2 O→15Fe2+ + 2SO4 2− + 16H+ (7)
The acid generated in the oxidation of sulfides can be neutralized at
the deposit site by attenuators contained in the mine tailings, for
example carbonates (reaction (8)) and silicates (reactions (9) and (10)).
CaCO3 (s) + H+ →Ca2+ + HCO3 − (8)
CaAl2 Si2 O8(s) + 2H+ + H2 O→Ca2+ + Al2 Si2 O5 (OH)4 (s) (9)
CaSiO3(s) + 2H+ + H2 O→Ca2+ + H4 SiO4 (10)
Acid production via sulfide oxidation is known as the acid potential
(AP), while the amount of acid that can be neutralized by attenuators is
denominated the neutralization potential (NP). In other words, NP
determination involves a neutralization reaction with acid (typically
hydrochloric acid), while the quantification of AP requires total sulfur
(in the form of sulfide ion) and sulfur in the form of sulfate, to obtain the
net sulfur responsible for the generation of acid. According to Eq.1, one
gram of sulfur present in one kilogram of mine tailings correspond to
3.125 g of CaCO3 to neutralize the generated acid.
( )
AP = %S2− − %Ssulfate *3.125 (Eq. 1)
2
Minerals Engineering 191 (2023) 107979
For the above mentioned, reactions (11) and (12) show the stoichi­
ometry for AP and NP process considering that CaCO3 and FeS2 are the
main species to consume and generate acid, respectively.
CaCO3 (s) + 2HCl →CaCl2 + H2 O + CO2 (11)
4FeS2 + 8CaCO3 + 15O2 + 6H2 O →4Fe(OH)3 (s) + 8SO2−4 + 8Ca2+ + 8CO2
(12)
According to SEMARNAT (2003), a NP/AP ratio less than 1.2 in­
dicates that the mine tailings have a high potential to generate acid
drainage, which leads to PTEs dissolution. Therefore, to prevent such
dissolution, it is necessary to add a neutralizing agent such as CaCO3, Ca
(OH)2, CaO, Al (OH)3, Na2CO3 or NaOH to the mine tailings (Park et al.,
2019). On the other hand, a ratio of NP/AP > 1.2 indicates the abun­
dance of attenuators, so these tailings do not have the potential to
generate acid drainage and there is a very low risk of PTEs dissolution.
Regarding the chemical analysis to quantify the metal content,
sequential extractions or selective sequential extraction procedures have
been used to study elements speciation in soils, sediments, and mine
waste (Tessier et al., 1979; Dold and Fontboté, 2002, 2001; Sondag,
solid material in contact with a series of appropriate chemical solutions
of increasing aggressiveness (reactivity strength, Table 2) that represent
the possible environmental conditions at the deposition site and aims to
simulate the release (dissolution) of the elements such as EPTs. The
contact between the solid and the chemical solutions can be carried out
sequentially or non-sequentially (parallel). The first technique starts
with a fixed amount of solid in stage 1, and the undissolved solid be­
comes part of the next stage. On the other hand, in parallel mode, a fixed
amount of solid material is contacted in each of the chemical solutions
regardless of the order of the stages; assuming that each chemical so­
lution corresponding to a given stage dissolves the elements of the
previous stages.
Due to the health risks associated with PTEs dissolution, it is very
important that a detailed assessment of the acid drainage potential and
particle size of mine tailings should be carried out to establish an
environmental remediation strategy, which beyond the scope of this
research.
The study of the dissolution of elements by sequential extraction,
especially base metals (Pb, Cu and Zn) and precious metals (Au and Ag)
metallurgical process for their recovery, giving added value to this type
of waste to be used as raw material in the mining industry (Nwaila et al.,
2021a). On the other hand, knowledge of the silicon content opens the
opportunity to use mine tailings as additives in the production of mor­
tars for the construction industry (Kuranchie et al., 2015).
Based on the previous paragraph, this work presents the character­
ization of a representative sample of mine tailings from the state of
Zacatecas, in order to determine its granulometry and potential as an
acid drainage generator. In addition, a dissolution analysis of Cu, Fe, Pb,
Ca and Zn through sequential extractions, as well as a metallurgical
process of leaching-solvent extraction-electrolysis to obtain metallic
copper at room temperature and pressure in Mexico City (20 ◦ C and 79
kPa).
2. Material and methods
2.1. Characterization of mine tailings
The tailings sample was collected in the state of Zacatecas, using a
manual cone and quartering technique, to obtain a representative
sample of approximately 12 kg. The entire sample was separated by
particle size using sieves and approximately 0.2 g of the fractions were
digested with aqua regia (75% HCl and 25% HNO3). The liquors ob­
tained were analyzed by Atomic Absorption Spectrometry (AAS, Varian
A. Ruiz-Sánchez et al.
SpectrAA220fs) or Microwave Plasma Coupled Atomic Emission Spec­
trometry (MP-AES, Agilent 4210). These chemical analysis techniques
(AAS and MP-AES) were also used to quantify the metal concentrations
in the leaching liquors, as well as in the aqueous phases of the solvent
extraction and in the electrolysis solution, respectively.
2.1.1. Analysis by X-ray fluorescence (XRF)
For the analysis by XRF approximately 100 g of the tailings sample
were carefully ground in an agate mortar to a particle size of less than
38 µm (400 mesh). The sample was analyzed on the portable Olympus
Delta XRF Analyzer using the Geochem mode.
2.1.2. Analysis by X-Ray diffraction (XRD)
For the analysis by XRD approximately 5 g of the tailings sample
from the XRF analysis was packed tightly into an acrylic sample holder.
The analysis was carried out in a D8 Advance diffractometer in the range
of 4◦ -90◦ for the angle 2θ, at a speed of 8◦ /min. The identification of the
mineralogical phases was achieved using the Diffrac Eva 5.0 software.
2.1.3. Analysis by scanning electron microscopy (SEM)
For the analysis by SEM approximately 5 g of the tailings from the
XRF analysis were mounted on a cylindrical specimen of low-density
epoxy resin. The specimen was polished with silicon carbide sand­
paper with different grain sizes (200, 800 and 1200) until a mirror-like
finish was obtained; this was then coated with graphite to increase its
conductive properties. The analysis was carried out in an XL30 Phillips
electron microscope coupled to a microanalysis system with Energy
Dispersive Spectroscopy (EDS). The analysis conditions were 20 kV,
SS50 and WD 10 mm.
2.1.4. Determination of pH and electrical conductivity
The pH and electrical conductivity were measured as follows: in a
500 mL beaker, 30 g of mine tailings were added with enough deionized
water to obtain a pulp density of 100 g/L. The slurry was maintained in
suspension for 10 min with a marine propeller at 400 rpm. The slurry
was carefully filtered, and the filtrate was collected to measure the pH
and electrical conductivity using a previously calibrated Orion® Star
A215 Benchtop pH/conductivity meter.
2.1.5. Determination of iron in the form of pyrite
Sulfide in coals, sediments, minerals, and soils can be determined by
digestions with nitric acid, hydrochloric acid, or aqua regia (Petersen,
1969; Edwards, 1982). In this investigation, the estimation of the pyrite
content in mine tailings was carried out in the following three tech­
niques: (i) 0.2 g of the tailings sample from XRF were digested in aqua
regia (25% HNO3-75%HCl). An additional 0.2 g of the same sample was
digested with only concentrated HCl. The liquors from these digestions
were analyzed by AAS. The difference between the iron concentration
readings was considered pyritic iron. (ii) 0.2 g of the sample was
digested using hydrochloric acid to remove all iron excepted the pyrite
and organic sulfur. One more sample of 0.2 g was digested in nitric acid
to dissolve all iron forms including pyrite and sulfur dissolved in chlo­
ride acid. The difference between the iron concentration readings
determined by AAS in the digestion liquors was considered pyrite as
described in the norm NMX-B-021-1982, and (iii) by semi-quantitative
analysis based on the reference intensity indices (RIR) tabulated using
the Diffrac Eva 5.0 software. As a comparative test, the same procedure
was carried out using a mineral concentrate with approximately 33%
iron in the form of pyrite.
2.1.6. Acid potential (AP) and neutralization potential (NP)
The AP and NP tests were performed using the modified acid-base
balance test (PM-ABA) suggested by Lawrence and Wang (1997),
which is described in NOM-141-SEMARNAT-2003. For this, 1.5 g of
sample and 4 drops of HCl at 25% v/v were placed in contact on a watch
glass, observing and recording the degree of effervescence (release of
3
Minerals Engineering 191 (2023) 107979
carbon dioxide as a result of the reaction of calcium carbonate and hy­
drochloric acid) as null, low, moderate or strong. Afterwards, 2 g of
sample were placed in a 250 mL flask with 90 mL of deionized water and
a constant stirring (magnetic stirrer) of 400 rpm. In the flask, the vol­
umes of 1 N HCl were added at the times indicated in Table 1. After 22 h,
magnetic stirring was stopped, and the pH of the liquor was measured. If
the pH of the liquor is greater than 2.5, adjust the pH to a value of 2.
However, if the pH is less than 2, repeat the test. Magnetic stirring was
maintained for two additional hours, ending the test with the titration of
excess HCl with 0.1 N NaOH.
The NP value (g CaCO3/kg) was determined from the stoichiometry
corresponding to reaction (11), which indicates a proportion of 1.37 g of
CaCO3 per gram of HCl consumed when neutralizing one kilogram of
mine tailings. On the other hand, the AP (g CaCO3/kg) was determined
from the approximation of the total pyrite content (section 2.1.5) and
the stoichiometry of reaction (12), which indicates a ratio of 1.67 g
CaCO3 per gram of FeS2 for each kilogram of mine tailings.
2.1.7. Sequential extractions
The sequential extractions in this research were carried out accord­
ing to the methodology of Parviainen (2009), adapting this series of
chemical solutions to an initial calculation base for 20 g of tailings
(Table 2), adding a sixth stage that consists of digestion of the solid
residues from step 5 using aqua regia. In each of the stages, careful
filtration was carried out to avoid the loss of undissolved solid residues.
The liquors from each sequential extraction stage were analyzed by AAS
or MP-AES to determine the concentrations of Fe, Cu, Pb, Zn, As and Ca,
while the solid residues recovered in each of the filtrations were dried in
an oven at 60 ◦ C for 24 h. It is important to mention that in each stage of
the sequential extraction approximately 1 g of dry solid residue was
taken to be analyzed by XRD and SEM.
2.2. Hydrometallurgical process for copper recovery
In the hydrometallurgical process for the recovery of metallic cop­
per, the following reagents were used: hydrogen peroxide (34% w/v, J.T
Baker), purified ethylene glycol (17.88 M, J.T Baker), sulfuric acid (98%
purity, J.T Baker), ethylenediaminetetraacetic acid disodium salt dihy­
drate (99.9% purity, J.T Baker), oxalic acid dihydrate (99.5% purity, J.T
Baker), Millipore deionized water prepared on a Milli-Q system (with a
conductivity of 18 MΩ.cm a 25 ◦ C) and a 10% by volume Acorga M5774
(5-Nonyl-2-hydroxy-benzaldoxime, CYTEC) extraction solvent solution
prepared with kerosene.
2.2.1. Copper leaching
The leaching tests were carried out in a cylindrical stainless-steel
reactor with a capacity of 0.3 L and 4 vertical baffles. The reactor was
coupled to a temperature control system composed of a recirculating
bath (Haake DC10) with cooling water, a stainless-steel coil, and a
mechanical stirring system coupled with a Rushton turbine-type stirrer
rotating at a speed of 400 rpm. Each of the leaching tests was performed
at 20 ◦ C and 79 kPa (temperature and atmospheric pressure in Mexico
City) for a period of six hours, using 200 mL of each of the leaching
solutions shown in Table 3 and the mass of mine tailings necessary to
obtain an initial pulp density of 100 g/L. During the leaching progress,
aliquots of 5 mL were drawn at 30-minute intervals; these aliquots were
Table 1
Addition of HCl for the determination of NP.
Degree of effervescence Volume of 1 N HCl (mL)
0h 2h
Null 1 1
Low 2 1
Moderate 2 2
Strong 3 2
A. Ruiz-Sánchez et al. Minerals Engineering 191 (2023) 107979

Table 2
Summary of the six-step sequential extraction.
2.2.3. Copper extraction
For the extraction stage, different O/A ratios were employed,
Name Procedure PDM Reference
maintaining a constant total volume of O (mL) + A (mL) equal to 15 mL
Stage1. “Water 20 g of sample into Water-soluble Dold (2003) and a pH = 2 value for phase A. Copper in aqueous phase A was
soluble” 1000 mL deionized fraction, secondary determined by AAS or MP-AES and the percentage of copper enrichment
H2O shake for 1 h at sulfates, e.g.,
RT gypsum
was determined from the ratio of the residual and initial concentrations
Stage 2. “AEC” Residue 1 + 500 mL Adsorbed and Hall et al. for the aqueous phase.
(0.25 M CH3COONa exchangeable ions, (1996)
+ 0.26 M carbonates 2.2.4. Copper stripping
CH3COOH) shake
Once the O/A ratio that allows the greatest extraction of copper
for 6 h at
Stage 3. Residue 2 + 400 mL Amorphous Fe (III) Dold (2003) (point 2.2.3) was determined, the corresponding stripping was con­
‘‘Fe(oxy) of 0.2 M precipitates, e.g., ducted by contacting the copper in the form R2Cu (org) with a solution
hydroxides’’ (NH4)2C2O4 shake schw, fer, jt, go, of sulfuric acid (2H+ in reaction (14), which in this case corresponds to
for 1 h in the dark, MnO2 the aqueous phase A) to strip copper.
at RT
Stage 4.‘‘Fe Residue 3 + 400 mL Residual Fe(III) Dold (2003) R2 CuOrg + 2H + 2+
(14)
aq ↔ Cu(aq) + 2RHOrg
oxides’’ of 0.2 M precipitates (e.g., go,
(NH4)2C2O4 in jt) and primary Fe The percentage of copper stripped from the organic phase was
water bath at 80 and (II) oxides (mgt,
shake for 2 h hem)
determined from a balance between the initial total copper content in
Stage 5. Residue 4 + 15 g of Primary and Hall et al. the organic phase and the copper concentration in the aqueous phase.
‘‘Sulfides’’ KClO3 and 300 mL supergene sulfides (1996) and
of 12 M HCl, 200 mL and organics Dold (2003)
2.3. Copper electrowinning
of 4 M HNO3, water
bath at 90 ◦ C for 20
min Copper electrowinning was carried out using the copper-rich
Stage 6. 0.1 g + 25 mL of Sillicates, residual In this aqueous solution obtained from copper stripping stage. An electrolysis
‘‘Digestion’’ HCl + 75 mL of solid investigation cell was installed consisting of a power source, a graphite anode and a
HNO3 at boiling
point and stirring
stainless-steel cathode with an area of 21.12 cm2. 200 mL of the solution
with magnetic stir were placed in a cylindrical container with a capacity of 250 mL. The
bar two electrodes were connected to the power source (Triple Output
PDM: preferential dissolved minerals, RT: room temperature, schw: schwer­
programmable DC power supply), through which a current of 0.3 A was
mannite, fer:ferrihydrite, jt: jarosite, go: goethite, mgt: magnetite and hem: applied for a period of 6 h. During this time, 1 mL samples of the solution
hematite. were taken every 15 min, which were diluted with deionized water
before quantifying the remaining copper in the aqueous solution.

Table 3 3. Results and discussion

Leaching solutions for the dissolution of copper in mine tailings.
Leach solution Label 3.1. Characterization of mine tailings: Granulometry and metal content
0.007 M H2 SO4 LS1
0.007 M H2 SO4 , 1 M H2 O2 y 0.2 M EDTA* LS2 Fig. 1a shows the distribution of the percent retained (100*mass
0.007 M H2 SO4 y1MH2 O2 LS3 retained in each sieve/total mass) corresponding to the 12 kg of mine
* ethylenediaminetetraacetic acid. tailings used to carry out this investigation. As can be observed, 18.2% of
the tailings have a particle size of less than 50 µm, while 17.2%, 19.2%
and 17.4% correspond to sizes of +50 µm, +75 µm and +94 µm,
filtered, and 1 mL of the filtered solution was diluted in a 1:10 volu­
respectively. Consequently, 28% of the tailings contain particles with a
metric ratio with deionized water prior to quantifying the Fe, Cu, Pb, Zn,
size in the range of 150 µm − 425 µm. Based on the percent retained
As and Ca concentrations. The remaining filtrate was reincorporated
(Fig. 1a), the average sizes P50 = less than 90 µm and P80 = less than170
into the reactor. After six hours, the resulting leach liquor was filtered
µm (Fig. 1b) corresponding to the cumulative percentage passing of 50%
and the solid residue was analyzed by XRF, XRD and SEM as described in
and 80% of the tailings, respectively, were estimated. The granulometry
points 2.1.1, 2.1.2 and 2.1.3, respectively.
(Fig. 1a and b) suggests the following: firstly, it is confirmed that these
To improve the leaching stage of the metallurgical process, addi­
tailings are a human health threat since 18% are fine particles (particle
tional leaching tests were carried out at 0.007 M H2SO4 with pulp
size < 50 µm), which can be easily carried by the wind and enter the
densities equal to 200 and 300 g/L. In addition, one more leaching
respiratory system. Secondly, 50% of the tailing had an average size of
experiment was performed with 0.21 M H2SO4 and 300 g/L.
less than 90 µm, which is favorable for a leaching process without the
The percentage of dissolved metal in the sequential extractions and
need to reduce the particle size through grinding.
leaching tests was determined from the ratio of the content (in mg) of
Fig. 1c and 1d show the content of Cu, Pb, Zn, Ca, As and Fe in the
each in the liquor and the initial amount (in mg) present in the mine
mine tailings. These results demonstrate a wide variation between metal
tailings sample.
content and particle size, thus confirming the heterogeneity of mine
tailings. On the other hand, it is important to mention that the con­
2.2.2. Copper purification by solvent extraction
centrations of Cu (>5000 mg/kg), Pb (>1000 mg/kg), Zn(>6000 mg/
The leaching liquor obtained in section 2.2.1 (aqueous phase A)
kg), As (>1000 mg/kg), Fe(>11000 mg/kg) and Ca (>5000 mg/kg)
containing Cu+
2 (aq), was contacted with an organic solution (Phase O)
exceed the limits established in NOM-141-SEMARNAT-1993, which
composed of 10% volume of Acorga 5774 extractant and 90% kerosene
suggests that these residues represent a health risk. However, it is very
(RH, reaction (13)) to enrich copper, through the reversible reaction
important to emphasize that the actual dissolution value of the PTEs will
shown below.
depend on the generation of acid at the deposition site as a consequence
Cu2+ +
(aq) + 2RHOrg ↔ R2 CuOrg + 2H aq (13) of the oxidation of the sulfide promoted by oxygen, moisture, and
microorganisms.

4
A. Ruiz-Sánchez et al. Minerals Engineering 191 (2023) 107979

Fig. 1. (a) Percent retained, (b) cumulative percent passing, and (c, d) metallic composition corresponding to the particle size test in the mine tailings sample.

Fig. 2 shows the distribution of the total content of Cu, Fe, Pb, Zn, As
and Ca in the sample of mine tailings. As can be seen, approximately
20% of the total concentration for each metal is found in the coarse
particles (177–425 µm). Therefore, about 80% of the metal content is
distributed in particles smaller than 177 µm; so this information opens
the possibility of taking advantage of this mining residue from a hy­
drometallurgical process for the recovery of metals, since it does not
require reduction of particle size and therefore the economic costs
associated with grinding are avoided.
The heterogeneity in the metallic composition of the mine tailings
(Fig. 1c and Fig. 1d) can also be observed in Table 4, where the
analytical composition is shown for a random tailing sample. Due to the
heterogeneity in the metallic composition for mine tailings, an average
metallic composition (%wtj ) was estimated for the sample using the
equation (2), where n corresponds to each of the 7 particle sizes, %wj is
the percent retained for the fixed particle size n (Fig. 1a) present in the
mineral concentrate, and %wtj represents the metallic composition for
each particle size (Fig. 1c and 1d). The results of this estimation show
that the average metal content for Cu, Pb and Zn can be approximated to
the analytical concentration with an underestimation (with respect to
the chemical analysis by AAS) of approximately 1.33%, 2.7% and
13.2%, respectively.

Table 4
Metal content in mine tailings for a random sample quantified by AAS and XRF.
Metallic content, mg/kg

Element AAS XRF Average from equation (2)

Cu 6000 6332 5920

Fe 210,000 198,500 153,500
Pb 1470 1350 1430
Ca 75,900 83,000 71,200
Zn 8960 7415 7770
As 1520 1425 1450
Cd 74.5 – 71.8
Si – 36,200 –
Al – 4600 –
Mn 1325
Fig. 2. Distribution of the total content of Cu, Fe, Pb, Zn, As and Ca in different
– –
P – 1000 –
particle sizes for the mine tailings sample.

5
A. Ruiz-Sánchez et al. Minerals Engineering 191 (2023) 107979

∑
n
%wj Table 5
%wtj = .%wtj (Eq. 2) Pyrite content in mine tailings, determined by chemical methods.
j=1
100
Sample Iron content (%)
One more way to estimate the average metallic composition was an
HNO3 HCl Pyritic iron Pyrite content (%)
XRF analysis (Table 4). This analysis is non-destructive and is done
quickly. According to the concentrations in Table 4 by means of XRF, an Mine tailings 10.8 9.2 1.6 3.2
Reference (33% FeS2) 23.3 8.9 14.4 29.6
overestimation of the order of 6% is obtained for Cu and an underesti­
Aqua regia HCl Pyritic iron Pyrite content (%)
mation of 8% and 17% for Pb and Zn, respectively. Mine tailings 11.2 9.4 1.8 3.7
The diffractogram (Figure S1 of the supplementary material) corre­ Reference (33% FeS2) 24.4 9.2 15.2 32.5
sponding to a semi-quantitative analysis of the mine tailings sample
shows the presence of 22% ferriian hibschite (PDF-01-072-8446), 40%
andradite (PDF-01-089-7563), 12.5% microcline (PDF-01-071-0955), corresponding to stage 5 in Table 2, are necessary for pyrite dissolution
7.6% quartz (PDF-00-046-1045), 5% calcite (PDF-01-083-1762), 8.4% as shown in Fig. 4.
maghemite (PDF-00-039-1346) and 4.5% pyrite (PDF-00-042-1340) as The pH value = 7.26 shown in Table 6 is in accordance with the low
the principal mineral phases, which provide the abundant amount of Fe, alkalinity present (NP = 14.75 kg CaCO3/ton) while the low conduc­
Al, Mn, Ca and Si shown in Table 4. No phases were found minerals that tivity (463 µS/cm) suggests an almost zero total concentration of soluble
can be attributed to the content of Cu, Pb, Zn, As and Cd, probably salts, therefore, according to the NOM-021-SEMARNAT-2000 standard,
because these mineral phases are below XRD detection limit. On the the mine tailings sample is classified as neutral and without saline
other hand, the two SEM micrographs (Fig. 3) confirm firstly the het­ effects.
erogeneity in particle size and secondly; the abundance of iron (red
color) and silicon (green color) from silicates (ferriian hibschite, 3.1.1. Sequential extractions
andradite, microcline) and quartz. Fig. 5 shows the percentages of total metal dissolved in each of the
The lack of sulfur (blue color) in the mapping of Fig. 3 confirms the stages corresponding to the sequential extractions. In stage 1, the
low content of pyrite determined by chemical methods (3.2% and 3.7% dissolution percentages for Cu, Fe, Pb, Ca and Zn were less than 0.05%.
according to Table 5) or 4.5% estimated by semiquantitative analysis The liquor of this solution had a concentration of approximately 500
(Fig. 1 of the supplementary material). mg/L of Ca. This solution was contacted with a barium chloride solution.
The pyrite content in the mine tailings sample was approximately The lack of a barium sulfate precipitate indicates that dissolved calcium
similar in the three estimation methods; however, in the case of the is present in the form of calcium carbonate (Figure S1 of the supple­
chemical methods there is a difference of 0.5%, probably due to the fact mentary material) as reported by Salas (2014) and not in the form of
that aqua regia is chemically more aggressive and therefore, dissolves a calcium sulfate, as indicated in Table 2. In stage 2, 18% copper, 2.5%
greater amount of iron as seen in Table 5 for the reference sample. Based lead, 12.5% calcium and 8% zinc were dissolved. The addition of barium
on these results, the presence of at least 3% pyrite (equivalent to 30 g chloride showed no formation of barium sulfate, indicating that copper,
CaCO3/kg of tailings) in mine tailings is confirmed, but it is not possible lead, calcium, and zinc dissolved corresponds to phases in the form of
to establish which of the three methods is appropriate due to the dif­ carbonates. For example, dissolved calcium, which is still present in the
ference of the results could be due to the heterogeneity in the metal form of CaCO3 (Figure S2 of the Supplementary Material).
content of the mine tailings sample. In stage 3, only 7% of the total copper and 0.1% of zinc were dis­
The EDS analysis for the two micrographs in Fig. 4 show that pyrite solved, while in stage 4, where the same solution as in stage 3 was used
(Spectrum 16) is occluded in the abundant phases of silicates and quartz at a higher temperature, 48% of copper was dissolved, 5 % iron, 12%
(Spectrum 15), so that despite the fact that the NP/AP = 0.24 ratio lead and 12% zinc, respectively. In stage 5, 25% Cu, 50% Fe, 65% Pb,
(Table 6) suggests the generation of acid drainage and as a consequence, 15% Ca and 18% Zn were probably dissolved as sulfides. Finally, in stage
a high risk of PTE dissolution. However, the almost negligible amount of 6, which corresponds to digestion in aqua regia at its boiling point, the
free pyrite implies that its oxidation will occur slowly because silicates remaining 45% Fe, 19% Pb, 72% Ca and 61% Zn were dissolved.
are acid attenuators and because of the difficulty for oxygen to diffuse The experimental conditions of stage 6 are chemically more
through them. Furthermore, the sequential extractions (see section aggressive than those of stage 5, for which reason the two micrographs
3.1.1) confirmed that more aggressive chemical conditions, in Fig. 6 corresponding to the residues of stage 5 show a hollow space in
the silicate (spectrum 6) due to dissolution of the initially occluded

Fig. 3. SEM micrographs corresponding to the mapping for the location of iron (red), silicon (green) and sulfur (blue). Zoom in on the file to better see the blue dots
in the image. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

6
A. Ruiz-Sánchez et al. Minerals Engineering 191 (2023) 107979

Fig. 4. SEM micrographs corresponding to the pyrite contained in the mine tailings sample. Zoom in on the file to better see the blue dots in the image. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

(spectrum 9 in Fig. 6, and Figure S5 of the supplementary material).

Table 6
Therefore, the metals leached in stage 6 can be attributed to the disso­
Some physical and chemical parameters for the mine tailings sample.
lution of the mineralogical phases present, as well as the silicates (fer­
Parameter Value riian hibschite, andradite, and microcline).
pH 7.26 ± 0.02 The results of the sequential extractions showed that mine tailings
Electric conductivity (µS/cm) 463 ± 1.8 can be used as raw material for the recovery of metals, such as copper,
NP (g CaCO3/kg) 14.75 ± 0.68*
lead and zinc. However, the dissolution of lead and zinc requires
AP (g CaCO3/kg)* 61.5
NP/AP ratio 0.24 aggressive chemical solutions such as those used in stages 5 and 6, which
makes it difficult to recover them through a hydrometallurgical process
*Estimate considering 3.7% FeS2 obtained by chemical method.
since it will involve the dissolution of almost all metals and would most
likely complicate purification of any of them. In contrast, the dissolution
of approximately 80% of the total copper requires moderate chemical
conditions, for which a hydrometallurgical process was proposed to
recover it.
It is important to mention that despite performing a sulfur mapping
in the SEM characterization, no mineralogical phases were found in the
form of sulfide for copper, lead and zinc. This can be explained if Cu, Pb
and Zn are actually in the form of oxides, carbonates, sulfates, and hy­
droxides, but occluded in the abundant of silicates and quartz, so it is
reasonable that their dissolution requires first attacking the matrix of
silicates and quartz, to facilitate the access of the leaching medium. The
aforementioned is confirmed by the dissolution (Fig. 5) of approxi­
mately 60%, 60% and 20% of zinc, lead and copper, using the chemical
solutions corresponding to steps 5 and 6, respectively. This agrees with
the two SEM micrographs in Fig. 7 corresponding to residues from stage
4 where the joint presence of Cu, Si, Mg, Fe and O is observed, as well as
the presence of lead sulfate. Other evidence in this regard can be seen in
Figure S8 of the supplementary material.
Fig. 5. Percentage of dissolved metals in the sequential extractions of Based on the previous paragraph, an estimate of the distribution of
mine tailings. total copper was made (Table 7) considering the mineralogical phases
mentioned in Table 2, suggesting that copper is in the form of carbon­
pyrite that was not identified by diffractograms or mapping (Figure S3 ates, oxides, and sulfides (despite not identify a copper sulfide), which
and S4 of the supplementary material); while the residues of stage 6 contribute 27, 53 and 20% of the total copper, respectively. Therefore,
show the dissolution of most of the silicates, leaving mostly silica the composition of the mine tailings was estimated to be approximately

7
A. Ruiz-Sánchez et al. Minerals Engineering 191 (2023) 107979

Fig. 6. SEM micrographs corresponding to stages 5 and 6 of the sequential extractions.

Fig. 7. SEM micrographs corresponding to stage 4 of the sequential extractions.

2.5% carbonates, 6% oxides and hydroxides, 20% in the form of sulfides,
70.5% silicates, and 1% quartz.
To end this section, it is very important to mention that despite the
heterogeneity in the metal content in the mine tailings, a consistent mass
balance (except iron) was obtained in the sequential extractions
(Table S1 of the complementary material). In other words, the metal
content was similar when performing a digestion analysis for a random
sample of mine tailings, with that obtained by adding the concentrations
of each of the stages of the extraction sequence. The difference in the
mass balance for the case of iron is due to the fact that the sequential

8
A. Ruiz-Sánchez et al.
Table 7
Distribution of the mineralogical phases of copper in the mine tailings sample.
Mineral phase Composition Total copper
Carbonates 2.5 27
Hydroxides/oxides 6 53
Sulfides 20 20
silicates 70.5 0
Quartz 1 0
extraction in stage 6 still contains abundant iron in the form of silicates,
unlike the direct digestion of 0.2 g of mine tailings where only quartz
remained.
3.2. Copper leaching
Based on the mineralogical distribution of the copper phases
(Table 7), three aqueous leaching solutions with moderate reactive
strength were proposed. The results in Fig. 8 show that the LS3 leach
solution achieved approximately 60% of the copper in 200 min, after
which time the leach essentially stops, probably due to the rapid
decomposition of hydrogen peroxide as a consequence of the Fenton and
Fenton-type reactions established between hydrogen peroxide and dis­
solved copper and iron (Ruiz-Sánchez and Lapidus, 2017; Ruiz-Sánchez
and Lapidus, 2022). In contrast, the LS2 solution yields 80% copper
leaching in 360 min, given that EDTA forms complexes with dissolved
copper and iron, impeding hydrogen peroxide decomposition (Ruiz-
Sánchez and Lapidus, 2018; Ruiz-Sánchez et al., 2020). The additional
20% of copper was not leached, probably because the mineralogical
phases of the rest of the copper are in occlusion in the silicates and
quartz as mentioned in point 3.1. On the other hand, the LS1 leach so­
lution shows that it is possible to recover approximately 76% copper in
360 min.
The copper leaching results suggest that the most appropriate
leaching solution in this case is LS1, mainly driven by the lower cost of
the sulfuric acid solution compared to hydrogen peroxide-sulfuric acid
(LS3 solution) and hydrogen peroxide solutions-sulfuric acid-EDTA
(LS2); even with LS2, copper purification would be difficult due the
elevated chemical stability of Cu(II)-EDTA complexes.
Subsequently, the effect of pulp density on copper dissolution was
evaluated in the LS1 solution. The results (Fig. 9) show that the increase
in pulp density of 100, 200 and 300 g/L, the percentage of leached
copper decreases from 76 to 55 and 33%, respectively.
Unlike the rapid growth in percentage of copper leached for 100 g/L,
the increase in pulp density at 200 and 300 g/L shows a marginal in­
crease after 60 min for leached copper. This behavior is due to the rapid
Fig. 8. Copper and iron leaching using different chemical solutions and pulp
density equal to 100 g/L.
9
Minerals Engineering 191 (2023) 107979
Fig. 9. Copper leaching using different pulp densities at 0.007 M H2SO4.
consumption of sulfuric acid as shown in Fig. 9, where in 360 min an
increase of 30 to 70% in the percentage of leached copper is observed
when the concentration of sulfuric acid increases from 0.007 M to 0.21
M H2SO4.
Based on the results shown in Fig. 10, the pulp density of 300 g/L and
the concentration of H2SO4 0.21 M were selected, which results in a
leach liquor with the concentration and percentage of leached copper
that it shows in Table 8. According to Table 8, in the leaching process a
small percentage of Fe, Pb and Ca are dissolved, which agrees with the
diffractogram shown in Figure S6 of the supplementary material where
the initial sample as the solid residues of the leaching show the same
mineralogical phases of Figure S1 of the supplementary material.
Furthermore, pyrite practically does not dissolve in 0.21 M H2SO4, as
shown by the abundance of blue dots corresponding to sulfur mapping in
Figure S7 of the supplementary material.
In the leaching stage, it is not recommended to use a concentration
higher than 0.21 M H2SO4 because it increases the concentration of ions
other than copper and, consequently, can make the solution difficult to
purify.
3.3. Solvent extraction and electrolysis of copper
Fig. 11 shows the copper concentration in the aqueous phase in
contact with different O/A ratios. As can be observed, the increase in the
O/A ratio facilitates the extraction of copper from the aqueous phase (A)
to the organic phase (O); therefore, for extraction purposes, an O/A ratio
in the range of 0.2–1 is sufficient; under these conditions, 96% of the
Fig. 10. Percentage of dissolved metal at 300 g/L pulp density and different
concentrations of sulfuric acid.
A. Ruiz-Sánchez et al. Minerals Engineering 191 (2023) 107979

Table 8
Dissolved metal percentages and metal concentrations in the leach liquor.
Element Cu Fe Pb Ca Zn As

Leached (%) 68 1.3 1.8 0.35 31 23

Concentration (mg/L) 1226 450 90 600 580 120

Fig. 13. Copper concentration in the electrolyte phase (2 M H2SO4) for

different O/A ratios.

100
Fig. 11. Copper concentration in the aqueous phase during copper enrichment 90
using different O/A ratios. Initial pH in the extraction was 2.
80
Leached copper (%)
copper was extracted into the organic phase. The organic phase obtained 70
from an O/A ratio = 0.2 was considered for the next stage: stripping. 60
This organic phase was put in contact with a solution of sulfuric acid
50
(aqueous phase) at different concentrations, maintaining an O/A ratio =
1. The results (Fig. 12) showed that a concentration of 2 M sulfuric acid 40
produced an aqueous electrolyte containing 3750 mg/L of copper. 30
Additional experiments were carried out to determine the best O/A
20 0.007M H2SO4
stripping ratio with 2 M sulfuric acid (electrolyte phase). The results
(Fig. 13) show that an increase in the organic phase ratio for the copper 10 0.21M H2SO4
stripping copper with 2 M sulfuric achieved a solution rich in copper 0
with approximately 9200 mg/L of Cu and Pb, Zn, Fe, Ca, As concen­ 0 50 100 150 200 250 300 350 400
trations below 3 mg/L, which confirms that the Acorga 5774 extractant Time (Minutes)
is selective for copper.
Finally, Fig. 14 shows the copper concentration profiles in the elec­ Fig. 14. Copper concentration profiles in the 2 M electrolyte. Current density
trolysis cell; 60% of the copper was recovered in metallic form in 6 h of equal to 142 A/m2 for 6 h.
operation, with an average current efficiency of 86%.
Based on the results of this research, it is shown that mine tailings this, it was confirmed that the sequential extractions are important to
can be considered a value-added raw material to establish a metallur­ identify what reactivity strength the chemical solution must meet to
gical process that allows recovery of a metal of interest. In addition to achieve this purpose.

4. Conclusions

• The characterization of mine tailings by SEM, as well as the deter­

mination of NP, AP and sequential extraction, was essential to
determine the generation potential of acid drainage and facilitate the
identification of the metal to be recovered by hydrometallurgical
means.
• Although the NP/AP = 0.24 ratio indicates a potential for generating
acid drainage, the occlusion of 3.7% pyrite in silicates suggests a low
risk of PTE dissolution.
• The sequential extraction permitted identification of the metal phase
contained in the mine tailings and the possibility of its recovery with
a hydrometallurgical process using chemically moderate conditions.
• The Acorga 5774 extractant was selective for dissolved copper from
the pregnant leaching solution, achieving an increase from 1220 to
9200 mg/L in one stage, with small traces of Pb, Zn, Fe, Ca and As.
• This study may be applied to other mine tailings in order to evaluate
Fig. 12. Copper concentration in the aqueous electrolyte phase with different their potential for metal recovery (base metals or precious metals).
concentrations of sulfuric acid in a ratio of O/A = 1.

10
A. Ruiz-Sánchez et al.
CRediT authorship contribution statement
A. Ruiz-Sánchez: Methodology, Investigation, Writing – original
draft. Julio C. Juárez Tapia: Conceptualization. G.T. Lapidus:
Conceptualization, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
Ángel Ruiz Sánchez appreciates the financial support of the National
Council of Science and Technology (CONACyT) for the scholarship
awarded in the Call for POSTDOCTORAL STAYS FOR MEXICO: MO­
DALITIES 1 AND 2 to be held at the Autonomous University of the State
of Hidalgo (UAEH). Angel Ruiz Sánchez also thanks Professor María
Isabel Lázaro Báez for allowing access to the Hydrometallurgy labora­
tory of the Institute of Metallurgy, Autonomous University of San Luis
Potosí (UASLP) and the technical support of Francisco Galindo Murrillo,
Martha Imelda Franco Vázquez, Rosa Lina Tovar Tovar and Izanami
Lopez Acosta. The authors especially are grateful to Rosa Linda Tovar
Tovar for her valuable time to help in the careful analysis of RIR during
the review stage.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.mineng.2022.107979.
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