1. Introduction
Several studies have shown that mining activities can significantly damage, pollute and alter the environment (e.g., soil, sediments, water and air quality) as well as human health [
1,
2,
3,
4]. Furthermore, mining involves the creation of surface features that are unstable, prone to landslides and collapses, but, especially, expose the environment to exogenous vast areas of mineralized rocks and byproducts of mineral treatment. These outcomes produce significant changes in the chemical environment [
5,
6]. The large volumes of wastes produced by mining occupy huge areas; these accumulations can substantially change the original landscape.
Alongside mining, mining wastes, if managed properly, can be important to the economic growth of countries. The application of a proper treatment ensures environmental sustainability and minimize the risks to human health. In fact, the deposits of mining tailings should not be treated as inert wastes, but as a neo-mine: only a short-sighted vision would be limited solely to neutralize the harmful and toxic waste stored and to put in place procedures and interventions that allow the restoration of the original environmental conditions.
Instead, the enhancement of the tailings, in addition to the sale of raw materials grade high (precious metals such as gold), allows a complete and effective recovery of environmental conditions sustainable because the recycling activity also determines an economic convenience for the treatment.
Romania, like many other nations affected by a long history of mining, is now grappling with environmental and social issues related to tailings produced by mining activities. On the Romanian territory a total of 300 tailings deposits, produced by exploitation of different minerals, have been inventoried. All are of significant proportion and should be submitted to amelioration procedures, such as the neutralization of treatment residues [
7,
8]. These waste materials are a result of mining activities that have reached the end of the production cycle due to depletion of the reservoir or, after stopping of the process for environmental reasons (i.e., regulations put in place at the time of the Convention for Romania’s entry into the EU). In Romania, the administration of these landfills is carried out by the Romanian National Agency for Mineral Resources (ANMR). The mining sites considered within this study are Bălan, Deva deposit 1, Deva deposit 2, Brad Ribita and Brad Criscior. Mine Bălan, for example, which ceased its operations in 2006, under the Convention for the entry of Romania into the EU, is a tabular deposit tectonized in metamorphic rocks. The main mineral is chalcopyrite. The remaining reserves amounted to 500,000 tonnes at 0.8% of copper content. These reserves are substantially unavailable. The costs of re-mining and carrying out of modifications to enrich the mineral are too high compared to the value of resources and costs of extraction [
7,
8,
9,
10].
The deposits of tailings, left on the land during the mining of copper ore, contain 24.5 million tonnes of slag and more than 10 million cubic meters of materials that constitute a toxic and harmful waste. These deposits are located at a distance of few kilometers from the mining center (at the neighborhood of the Bălan town) [
7,
8].
The removable high-grade raw materials, from the tailings of Bălan, like those of the other mentioned sites, are:
industrial minerals, such as quartz, pyrite and chlorite, recoverable through metallurgical processes;
base metals, including copper and zinc, and precious metals such as gold and silver, extracted with hydrometallurgical processes.
The aim of this work is to apply innovative technologies for the treatment and exploitation of Romanian mining tailings. In particular, this study is focused on the development of an hydrometallurgical process for the recovery of gold from solid wastes of mining industry. The innovative treatment chosen was the thiosulphate process, that has advantages over the conventional cyanide and is non-toxic to humans; in fact, it is environmental impact is lower than for cyanidation [
11,
12,
13,
14,
15,
16,
17,
18].
The kinetics of the thiosulphate process has been studied with the main aim to improve the characteristics that distinguishes from the conventional cyanide process for gold recovery. The main potential advantages of this innovative treatment for gold recovery, can be summarized in the following points:
solubilization of gold with an appreciable rate of dissolution;
ammonia-containing solutions do not attack most of the gangue mineral constituents;
production of leach solutions, practically free of metallic elements that hinder the subsequent recovery operations;
ability to recirculate the ammonia leaching solutions;
non-toxicity of the reagents used in the leaching process;
possibility for recovery of the dissolved gold by known techniques, such as carbon adsorption and electrodeposition.
The greatest criticality of the process is constituted by the chemistry of the ammonia-thiosulphate system, that is very complicated due to the simultaneous presence of complexing ligands such as ammonia and thiosulphate, the Cu(II)–Cu(I) redox couple and the possibility of oxidative decomposition reactions of thiosulphate involving the formation of additional sulphur compounds such as tetrathionate [
11].
The ultimate purpose of this work is to develop a process scheme on the basis of results obtained at laboratory scale. This will be used to perform a preliminary study of the technical feasibility of process.
Figure 1 shows an example of a mining site with tailings from Romania.
2. Materials and Methods
2.5. Chemical Process
The study of the thiosulphate process, was conducted in mechanical stirred reactors made of Pyrex glass that have a capacity of 2000 mL. Leaching experiments were carried out to study the influence of the concentration of ammonia and the concentration of thiosulphate on gold dissolution, using reagents of analytical grade and distilled water.
The leaching solutions consist of sodium thiosulfate (Na
2S
2O
3∙5H
2O), used as active leaching agent, ammonia (NH
4OH 30%)—for the control of pH—and copper (II) sulphate (CuSO
4∙5H
2O)—which acts as an oxidant of gold [
11,
16,
17].
The tests were carried out at atmospheric pressure and room temperature, while the speed of mechanical agitation was kept constant at 400 rev/min. The leaching time was 4 h, the weight of the samples of 500 g, the particle size minus 80 μm, pH of 10.5 and a redox potential +0.1 V. At set time intervals, small volumes (10 mL) of leaching solution were taken from the reactor. These were analyzed to determine their Au content and, therefore for the kinetic study of gold dissolution [
19,
20].
The pH and the oxidation-reduction potential of the slurry, were measured using a combined glass electrode and a platinum combination electrode, respectively, both being connected to a digital pH meter.
At the end of each test, the reactor was emptied, while the filtration of the slurry was realized through pressure filters. The solid residue was submitted to washing with distilled water and ammonia; moreover, gold content was determined, after chemical dissolution of homogeneous and representative samples, with an Atomic Absorption Spectrometer (AAS Perkin Elmer mod. 460).
After leaching, the gold was purified by selective adsorption onto granular activated coconut carbon. The influence of the carbon concentration was studied.
This was conducted in Pyrex glass reactors of capacity of 2000 mL under mechanical stirring (400 rev/min), at room temperature, for a total contact time of 1 hour [
20,
21,
22].
The tests were carried out by placing in contact leached solution (500 mL) with the different amounts of coconut charcoal, an activated carbon material. The influence of the contact time was investigated by performing liquor withdrawals at set intervals. The concentration of the activated carbon was varied from 5 g/L to 15 g/L. After each experiment, carbon was recovered from the solution and left air drying. Representative samples of carbon were collected and submitted to quantitative chemical analysis.
The desorption of gold from carbon was carried out by elution with a water-ethyl alcohol solution prepared using absolute ethanol (C
2H
5OH) [
22]. The gold stripping tests were conducted in a Pyrex glass reactor, with a capacity of 250 mL. The reactor was fitted with three necks: the first one had reflux condenser for the removal of vapors, the second one housed a probe that was connected to a shaking-heating plate for stabilizing the temperature and a thermometer for temperature control was inserted through the third port. The tests were conducted varying the temperature from 40 to 85 °C.
Sampling was performed also at determined time intervals and then chemically analyzed to determine their Au content. These data were used to determine the kinetics of the process.
The final recovery of purified metallic gold from the water-alcohol solution, was carried out by the electrochemical process [
19,
20,
23].
Gold recovery conducted in an electrolytic cell with a capacity of 200 ml in a jacketed Pyrex glass, connected to a Julabo, mod. 5B thermostat (control from −20 to +100 °C). The cell was fitted with a saturated calomel reference electrode, a working electrode (cathode) constituted by a net of platinum wire, having a surface area of 100 cm2, and a counter-electrode (anode) consisting of a spiral platinum.
The cell was connected to a AMEL, model 555 B potentiostat-galvanostat. The current flowing through the cell was converted into a numerical value by an AMEL, model 721 integrator. The potential difference between the cathode and the anode was measured with an AMEL, model 631 differential electrometer.
The presence of a magnetic stirrer bar allows stirring of the solution into the cell. The electrolysis tests were conducted using 200 mL of strip solution.
4. Discussion
The preliminary study of the parameters and operating conditions for the various stages of the thiosulphate process shows, for the sample composed of mining wastes from Brad Ribita and Brad Criscior, the technical viability of the process. The experimental results obtained indicate good gold dissolution kinetics in the aqueous ammoniacal solution of thiosulphate, which can be used without special precautions and restrictions.
The gold extraction reached an average final value of 75% Au, working at room temperature, but, the trends for dissolution demonstrate that the thermodynamic parameters were not optimized, because gold recovery decreases during the best experiment. This fact, probably, is due to the thermodynamic instability of the complexing ligands (ammonia and thiosulphate) and oxidizing agents (copper ions) present in the system, tested for the first time on this type of material [
11,
24].
It is noted that the extraction of gold is already very high in the first 15 minutes: this is due to the gravimetric enrichment and means that a part of the gold is free and is not incorporated into the mineral matrix (see
Table 2).
Gold recoveries for the overall process including leaching (extraction yield of about 75% Au) and complete adsorption-desorption–electrodeposition cycle (about 90% Au recovered) were about 65–67% (considering the gold content in the washing) in line with the conventional cyanidation process, as demonstrated in previous experimental work [
25].
These results are very encouraging, considering that it is commercially an innovative process, applied to a gold ore with a low content.
Samples were leached after comminution <80 μm: a finer grinding would probably result in an increase in gold extraction, but its convenience can only be determined after careful cost analysis.
The optimization of the process is still required to identify the best process parameters and operating conditions. Considering the progressive depletion of gold mining reserves and the inability of the gold production to quickly react to the prospect of a change in prices and to changes in demand, it is providential to recover gold from mining tailings. The high price of the precious metal allows, as preliminary economic analysis shows, the feasibility of alternative processes despite the low levels of gold, the large amount of sterile to be treated and the high costs of extraction.
The enhancement of the tailings, in addition to the sale of raw materials of high grade, allows to implement an effective and sustainable recovery technology. In this way it is possible to guarantee over time the use of two indispensable resources of primary importance: the environment as a whole on one side and raw materials mining the other.
In addition to the economic and environmental aspects, we must consider the social benefits that the application of these innovative processes may generate such as providing many jobs and contributing thus to the development of repressed areas, improving the competitiveness of and creating added value and new jobs in raw materials processing, refining, equipment manufacturing and downstream industries.
In the next step of investigation, pre-treatment of components such as pyrite will be investigated before the extraction of gold. For this purpose a treatment circuit that employs biotechnological processes, with low energy consumption, will be integrated.
The elimination of pyrite will help to reduce the cost of extracting gold, reducing the consumption of the reagents. The application of physical-chemical and biological-chemical methods will allow the treatment of the Acid Mine Drainage, together with the recovery of heavy metals such as copper [
26]; moreover, the optimization of leaching kinetics will be performed. The complete leaching process analysis will be outlined, including detailed description of the process scheme together with the economic analysis.
Author Contributions
Conceptualization, F.V. and V.G.; Data curation, F.V. and D.G.; Formal analysis, S.U. and F.V.; Investigation, D.G.; Methodology, D.G.; Supervision, S.U.; Writing—original draft, S.U.; Writing—review & editing, S.U. and V.G.
Funding
The work was supported financially by the Istituto di Geologia Ambientale e Geoingegneria, CNR, through special funds for free theme research.
Acknowledgments
This experimental work was carried out during the course of the experimental degree thesis of Dr. Alessia Panone from Università degli Studi dell’Aquila. The authors are grateful to Dr. Alessia Panone and Mr. Pietro Fornari for their helpful collaboration during the experimental work.
Conflicts of Interest
The authors declare no conflict of interest.
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