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Article

Recovery of Noble Metals (Au, Pt, Ir, and Ta) from Spent Single-Use Medical–Technological Products

by
Evgenios Kokkinos
1,
Charikleia Prochaska
1,
Angeliki Lampou
1,
Effrosyni Peleka
1,
Konstantinos Simeonidis
2,
Georgios Vourlias
2 and
Anastasios Zouboulis
1,*
1
Laboratory of Chemical & Environmental Technology, Department of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
2
Department of Physics, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
*
Author to whom correspondence should be addressed.
Minerals 2024, 14(1), 90; https://doi.org/10.3390/min14010090
Submission received: 15 December 2023 / Revised: 9 January 2024 / Accepted: 11 January 2024 / Published: 12 January 2024

Abstract

:
Due to their unique properties, i.e., fluoroscopy response and inertness, noble metals and alloys are present in several widespread medical–technological products, such as catheters, guide-wires, and stents. Despite their value, these products serve as single-use consumables, following a fate of solid waste disposal and loss of their valuable metals. This work studies the development of a treatment methodology to recover noble metals such as Pt, Ir, Au, and Ta from certain commercial products commonly used for medical practices. In particular, a sequence of preliminary pyrolysis, aiming at polymer elimination, as well as an acid digestion step for selective metals dissolution, is suggested. Pyrolysis was capable of enriching samples with the targeted metals, though a small change in their oxidation states was observed. Still, acid digestion was fully able to successfully separate Au using a 50% v/v aqua regia solution for 30 min at room temperature and the Pt/Ir using concentrated aqua regia for 72 h under heating. Dissolution of Ta required a different leaching solution, i.e., a 50% v/v HF/H2SO4 mixture for 10 h under heating. According to the developed method, selective extraction of such noble metals in a concentrated slurry provides a high potential for the complete recovery and valorization of otherwise disposed medical wastes.

1. Introduction

Alongside commonly produced municipal and industrial wastes, for which numerous studies have been carried out concerning novel methods of management, the handling of specific medical and hospital waste streams also has also attracted the interest of scientific research. Nowadays, more and more people have gained access to the new technological products of advanced medicinal materials, and this implies a proportional increase in the amount of corresponding waste volumes [1]. Medical wastes are generally considered to carry a significant biological load, and for this reason, their management and disposal are governed by a large number of specific regulations, while any effort to reuse any of their constituents is currently prohibited or avoided [2]. The most-common methods of managing these wastes include sterilization/pasteurization and landfill disposal or incineration [3]. Nevertheless, some of these medical–technological products are specialized devices containing valuable metals; thus, different managing approaches to those applied for the other/general medical wastes should be considered [4].
Noble metals are an important category of valuable materials appearing in these single-use medicinal products. Their extensive use is related to advanced diagnostic techniques where their unique chemical characteristics, such as their inertness and visibility through fluoroscopy by an external observer/operator, are required [5]. Τhe most widespread medical–technological products containing noble metals are diagnostic electrophysiology catheters, diagnostic guide wires, and self-expanding stents. Such products contain Pt/Ir alloy marker bands [6], Au-coating media [7], and Ta marker dots at each edge [8], respectively.
Recovering noble metals from secondary sources (i.e., through properly recycled devices) can be an means of supplying a significant percentage of market needs since mining operations are struggling to match the corresponding high and ever-growing demand [9]. Predicting a further increasing need for noble metals to support technological advancements promotes the exploitation of alternative resources. To this end, the European Union’s directives to face the problem of critical metals scarcity suggest the consideration of secondary sources as primary ones [10,11]. The problem has become more intense since efforts to replace noble metals in some of their applications, e.g., in catalysts [12,13], had an insignificant impact on the commercial demand. Therefore, many studies focus on their recovery from industrial sludges [14], catalysts [15], and electric wastes [16]. The recovery of noble metals from medical devices has been limited to the recovery of Au from implantable devices that contain printed circuit boards (i.e., pacemakers) [17]. On the other hand, a multitude of methods have been developed to recover gold from electronic waste (e-waste) [18]. To the best of our knowledge, medical–technological products, such as catheters, guide wires, and stents, have not been yet included in this research trend.
Regarding the general medical waste streams, the replacement of incineration by pyrolysis, an alternative sterilization method, was formerly studied, proving that this treatment method is an environmentally friendly option that combines lower temperatures and heating periods, lower emission of pollutants, and a residual ash/material complying with the stringent health requirements for subsequent safe disposal [19]. On the other hand, pyrolysis has already been applied in the recovery of noble metals from electronic wastes using the remaining ash. The main advantage of this process is the absence of polymeric fractions in the residual ash, so the metals’ recovery may be achieved via the application of common hydrometallurgical or pyrometallurgical processes [20].
The most popular scenarios regarding the recovery of noble metals from the residual ash or directly from the raw waste are selective leaching and digestion, a sequence commonly included in the framework of hydrometallurgical processes. Specific leaching reagents may efficiently extract noble metals from other co-existing substances of the solid waste stream, especially when only one or two of them are targeted. Typically, the noble metals are dissolved in aqua regia, cyanide, or strong acids such as HNO3, HCl, and H2SO4 (Table 1), while the addition of oxidizing agents increases leaching efficiency [15]. However, when targeted metals are more than one, the acid digestion process is initially preferred before the implementation of selective leaching [16]. This preliminary dissolution results in higher recovery rates for all metals of interest, whereas the subsequent leaching reaches a higher purity level [9]. Selective extraction and adsorption via activated carbon and membranes are the most realistic for implementation technologies that were tested at a laboratory scale [21].
This work aimed to establish a sequential process for the recovery of noble metals contained in diagnostic medical–technological products such as catheters, guide wires, and stents. For this purpose, samples were first subjected to pyrolysis to remove the polymer coating and enrich noble metals, whereas an acid digestion/selective leaching process was optimized for their efficient separation from the solid waste. Various leaching solutions and experimental conditions were tested, aiming to obtain separate liquid streams of concentrated Pt, Ir, Au, and Ta solutions.

2. Materials and Methods

2.1. Samples

New (unused) commercially available medical–technological products were selected as reference samples for this study, including a diagnostic electrophysiology catheter with Pt/Ir marker bands (Boston Scientific, model Viking), a diagnostic guide wire with a Au coating on one edge (ev3 company, model Nitrex), and a self-expanding stent with Ta dots in both edges (ev3 company, model Protégé) (Figure 1). The mentioned samples supplied all the metals of interest in the simulated waste streams examined in this work. As a pre-treatment step, the parts containing the noble metals were separated by cutting them from the rest of the product in order to increase the percentage of wastes in Pt, Ir, Au, and Ta.

2.2. Pyrolysis

A digital laboratory WITEG muffle furnace model FHX-05(Witeg Labortechnik GMBH, Wertheim, Germany), has been used for the initial pyrolysis step. During the experiments, approximately 60 mg of Au-coated guide wire, 60 mg of the diagnostic catheter (including one Pt/Ir marker band of 11 mg), and 3 mg of the stent (including 2 Ta dots) were used as the simulated mixed medical waste stream. The initial content of noble metals in this waste stream was not possible to determine before digestion. Pyrolysis was carried out by placing each of the three samples in separate porcelain capsules covered by lids and equipped with an exhaust gas outlet hole, ensuring anoxic conditions. The temperature was set at 550 °C for 60 min, following the optimal conditions of our previous work [25].

2.3. Characterization

The JEOL JSM-7610F Plus Scanning Electron Microscope (SEM-JEOL, Tokyo, Japan), with an integrated X-ray energy dispersive spectrometer (EDS-JEOL, Tokyo, Japan) and Oxford Instruments AZTEC (Oxford Instruments, High Wycombe, UK) analytical system, was used in the present study to acquire the images of the morphology and the distribution of elements regarding the structure of samples before and after pyrolysis. X-ray photoelectron spectroscopy (XPS) measurements were also performed before and after the pyrolysis experiments using the Axis Ultra DLD system (Kratos Analytical Ltd., Wharfside, UK); monochromatic Al Ka radiation was used as the X-ray source. The pass energy was kept constant at 40 eV, and it was calibrated for charge-induced shifts, considering the C1s peak (originating from the surface contamination of carbon) to be at 284.6 eV. The concentrations of noble metals, as well as of the other measured metals, have been determined via flame atomic absorption spectrophotometry by using the Perkin–Elmer AAnalyst 800 instrument (Perkin-Elmer, Waltham, MA, USA).

2.4. Acid Digestion

The pyrolyzed samples were placed in a beaker under reflux conditions (fitting to the top of the beaker of a spherical flask containing water to act as a condenser) when longer periods of treatment time were needed, and a sand bath was used as a heating source. A volume of 10 mL (i.e., 1.23% w/v) of different inorganic acids or their mixtures was tested, including HNO3 (69% w/w by Supelco), HCl (37% w/w by Supelco), H2O2 (30% w/w by Supelco), HF (40% w/w by Supelco), and H2SO4 (95–97% w/w by Supelco), for the selective digestion of noble metals. This step aimed for the complete solubilization of the studied metals: Au, Pt, Ir, and Ta; hence, the experimental conditions, i.e., the combination and concentrations of the examined acids, time, and temperature, were adjusted, with 100% of them in the liquid phase. Complete dissolution was achieved by repeating the digestion process under extreme conditions, leading to zero concentrations of noble metals in the liquid phase. In addition, other potential metallic impurities, e.g., Fe, Cr, Ni, and Ti, were also taken into account; however, in this case, they were not considered as a criterion for the determination of optimal separation conditions. The conditions wherein the highest separation between the noble metals was achieved were considered to be optimal and selective.

3. Results and Discussion

3.1. Characterization of Samples

Although the specification data provided by the products’ manufacturers are commercially available, they was also verified at the laboratory by applying EDS analysis. According to the obtained data, the diagnostic catheter contains Pt/Ir alloy bands, with a metals concentration ratio equal to 10/1. These bands are wrapped over a supporting steel grid and coated with a plastic cover. EDS analysis (Table 2) revealed that the above-mentioned ratio was equal to 9.3 along with the existence of a significant amount of oxygen (14.1 ± 3.2 wt%), indicating the presence of oxidized forms of metals. XPS analysis confirmed that catheter bands contained both elemental and oxidized forms of Pt (Figure 2a) and Ir (Figure 1c). Pt peaks at 70.0 and 73.4 eV are attributed to the elemental form (88.9 ± 3.1 wt%); whereas at 71.5 and 74.9 eV, they are attributed to the respective bivalent form (11.1 ± 2.7 wt%) [26]. Moreover, Ir peaks at 59.5 and 62.4 eV are attributed to the elemental form (73.4 ± 3.5 wt%), while those at 60.6 and 63.9 eV are attributed to the trivalent form (26.6 ± 2.8 wt%) [27].
Regarding the diagnostic guide wire, this is based on a Ni/Ti alloy (nitinol) wire which was gold-plated only on one end; the rest was enclosed in a plastic cover. As before, the presence of oxygen was confirmed via EDS analysis (11.3 ± 2.7 wt%). According to XPS diagrams (Figure 2e), peaks at 84.0 and 87.7 eV are attributed to the Au elemental form (79.9 ± 2.7 wt%), while those at 84.9 and 88.4 eV are attributed to the monovalent form (20.1 ± 3.5 wt%) [28]. The self-expanding stent is also based on a nitinol grid with four Ta dots to be placed at each end. The oxygen content was obtained via EDS analysis (18.1 ± 3.8 wt%). XPS peaks of Ta (Figure 2g) at 21.6 and 23.5 eV are attributed to the elemental form (67.4 ± 3 wt%), while those at 22.4 and 24.9 eV are attributed to the bivalent form (32.5 ± 4.7 wt%) [29].
It is worth noting that the aforementioned description of the samples’ structure and metals distribution, alongside the presence of noble metals, was also confirmed via SEM-EDS analysis. Figure 3a shows the SEM images on the surface of Pt/Ir bands. The morphology of this material appears to be quite smooth, with few surface scratches, due to the metallurgical production process. EDS analysis verified the presence of Fe, C, and Cr in the steel grid of the catheter’s cable. The guide-wire-related SEM image in Figure 3c shows the presence of a lamina with spiral geometry and relatively good uniformity in the gold-plated area. The SEM image in Figure 3e shows the Ni/Ti alloy grid (outer circle); whereas the composition was verified via EDS and the Ta dots (inner circle).

3.2. Characterization of Pyrolyzed Samples

The percentage of solid residue and the corresponding mass loss of the samples after pyrolysis were calculated via Equations (1) and (2), and the results are summarized in Table 3.
% solid   residual = m p m i × 100 ,
% mass   loss = m i m p m i × 100 ,
where mp is the mass in (g) of the solid product after pyrolysis, and mi the mass in (g) of the initial solid sample.
Considerable mass loss is noticed for the samples containing plastic parts, while the mass loss for the metallic parts of samples ranged from zero (for the case of Au) to 7.02 wt% (for Ta). The observed variation in the color of the Ni/Ti alloy grid, which supports the Ta dots, from silver to violet after the application of pyrolysis, along with the possible oxidation of Ta, may be the reason for the relatively high mass loss of this sample. According to other researchers, the surface layer of the Ni/Ti alloy mainly consists of titanium oxide. The temperature, time, and heating rate used during this moderate-heat pyrolytic treatment have a direct effect on the characteristics of the titanium oxide layer, resulting in color variations in the examined metal part and, by extension, in the weight change [30]. A solid ash residue was obtained from the plastic parts of the examined samples, while the parts of samples containing the metals of interest seemed, macroscopically, to be unaffected. The SEM images of samples after pyrolysis (Figure 3b,d,f) revealed no distinguished differences compared to the SEM images of the initial samples (Figure 3a,c,e)—apart from some plastic residue—remaining on the surface of diagnostic guide wire (Figure 3d).
EDS analysis of pyrolyzed samples is summarized in Table 4. According to the measurements, oxygen content decreased only in the case of Au, i.e., its elemental form increased. Metals distribution in the XPS diagram (Figure 2f) verified the elemental Au percentage increase of up to 94.1 ± 1.6 wt% by the corresponding peaks at 84.0 and 87.7 eV. Its monovalent form decreased to 5.9 ± 1.8 wt%, as defined by the corresponding peaks at 84.8 and 88.4 eV. On the other hand, the trivalent (oxidized) form of Ir increased to 63.2 ± 3.6 wt%, as presented by the corresponding peaks at 60.4 and 63.4 eV; while its elemental form decreased to 36.8 ± 1.6 wt%, as shown by the corresponding peaks at 59.7 and 62.7 eV (Figure 2d). Pt and Ta also presented an increase in their oxidized forms, but a new metallic form was introduced in both cases. Regarding Pt (Figure 2d), 72.1 ± 2 wt% of its distribution is attributed to the elemental form (corresponding peaks at 70.9 and 73.6 eV), 17.2 ± 1.5 wt% to the bivalent form (corresponding peaks at 71.3 and 74.6 eV), and 10.7 ± 2.4 wt% to the tetravalent form (corresponding peaks at 73.0 and 76.5 eV) [16]. Moreover, 31.2 ± 2.8 wt% of Ta distribution is attributed to the monovalent form (corresponding peaks at 21.7 and 23.8 eV) (Figure 2h), 28 ± 2.6 wt% to the bivalent form (corresponding peaks at 22.7 and 24.8 eV), and 40.8 ± 2.6 wt% to the pentavalent form (corresponding peaks at 26.3 and 28.2 eV) [29]. Τhe increase in the oxidized forms of the metals, except for gold, was attributed to the anoxic conditions applied during pyrolysis and the presence of oxygen [31,32].

3.3. Separation of Metals

Pyrolyzed samples were digested via the addition of acidic mixtures, applying different experimental conditions and aiming to obtain separate streams with respect to the metals of interest. Initially, various acidic solutions were prepared to digest Au since it presents the lowest solubility among the examined metals. According to Table 5, the optimum acidic mixture was proved to be aqua regia 50% v/v. Nitric acid oxidized the elemental Au to its trivalent form, and the presence of hydrochloric acid fed Au3+ with chloride anions to form stable (dissolved) chloro-complexes, following reaction 3 [33]. The 100% dissolution yield of the optimum experimental conditions was verified via a second digestion step of resulting solid residue from the first stage using this time concentrated aqua regia; in this case, Au was not determined in the liquid phase. On the other hand, when concentrated aqua regia was used as the main digestion solution, although 100% of the Au was dissolved, a low concentration of Pt was detected (i.e., the concentrations of these metals in the liquid phase found 208 mg/L Au and <1 mg/L Pt, respectively). When hydrochloric and nitric acid were applied individually, the yield was found to be much lower, i.e., 30% and 20%, respectively. Based on the abovementioned mechanism, a second oxidizing reagent was tested, namely, H2O2, along with HCl [34]. In this case, only half of the Au was dissolved under these experimental conditions, noting, however, that the application of higher concentrations of acidic solution, as well as the reaction time, may increase the HCl/H2O2 digestion yield [35].
The free-from-Au digestion residual material was then subjected to the second dissolution process. The main acidic reagent was also aqua regia (HCl/HNO3), but the experimental conditions were different [36,37]. Since Pt and Ir solubility in acids is lower than Au, the concentrated aqua regia was used in this case, while the system was also subjected to heating at 90 °C [38]. The dissolution rate was rather low due to the small reactive surface area of examined catheter marker bands and to the side reaction of HCl with HNO3 [39]. As a result, the complete dissolution of Pt and Ir required multiple additions of concentrated aqua regia under these intensive conditions, and it was achieved after 72 h, following reactions 4 and 5, respectively [10]. In detail, every 6 h, 5 mL of the acidic reagent was added, while the reflux conditions did not allow the solution’s level to drop below 10 mL. The metals concentration in the liquid phase was found to be 653 mg/L Pt and 61 mg/L Ir, respectively. Regarding dissolution kinetics, metals concentration was also determined in 48 h (Table 6). In that case, the corresponding measurements were 449 mg/L and 43.6 mg/L, respectively. Pt and Ir are used as an alloy in marker bands and their dissolution is a slow reaction, so selective separation was not reached [23].
2Au + 11HCl + 3HNO3 → 2HAuCl4 + 3NOCl + 6H2O
3Pt + 18HCl + 4HNO3 → 3[PtCl6]2− + 6H+ + 4NO + 8H2O
3Ir + 18HCl + 4HNO3 → 3[IrCl6]2− + 6H+ + 4NO + 8H2O
Ta2O5 + HF/H2SO4 → TaF62−/TaF72−
The other examined materials in Pt/Ir digestion residue—besides the marker bands (i.e., the steel grid and nitinol)—were dissolved, and the only residue that was still left insoluble was the Ta dots from the stent. Aqua regia managed to dissolve a very small amount of Ta (<5%). This can be attributed to the precipitation of Ta again in the form of hydrated oxide (Ta2O5.5H2O) [40]. On the other hand, the combination of HF and H2SO4 (acid rate, 1:1; concentration, 50% v/v; temperature, 90 °C; and reaction time, 10 h) proved capable of its subsequent dissolution following reaction 6, as the metals concentration in the liquid phase was found to be 175 mg/L (Table 6) [24]. Tantalum forms stable complexes with fluoride, but when only HF 50% v/v was applied, the dissolution was very difficult (22%) [41]. Moreover, the use of the previous HF/H2SO4 mixture in a catheter’s Pt/Ir marker band (i.e., without the presence of other materials) can also dissolve some of the iridium (47.4%), but not the platinum (2.4%), as chloride ions were not present to form the respective stable chloro-complexes [42].

3.4. Economic and Environmental Aspects

The economically attractive approach of the separate management of single-use medical products containing precious metals has to overcome the lack of appropriate legislation and the lack of appropriate market-driven solutions. These constraints have encouraged the prevailing single-use and discharge culture. Therefore, such research efforts could motivate the policy changes and market-driven solutions needed to transform the way in which such single-use medical products are being managed.
With growing environmental awareness, increasing costs for raw materials, and the constant pressure on the health sector to reduce its operational costs, the existing linear management approach for single-use medical products, discharged without being further treated for precious metals recovery (Table 7), is reaching its limits [43].
Considering the weight of the precious metals-bearing parts examined in this study, their respective metal content (79–90% for Au and Ta; 90% for Pt and 10% for Ir), and the current market price for trading such metals, it is estimated that since 100% of the metal content is recovered, the money revenue in USD could be of 3.5 USD for each diagnostic electrophysiology catheter, 4 USD for each diagnostic guide wire, and 0.1 USD for each self-expanding stent. The money revenue could come to millions of US dollars each year, taking into consideration that every year, only the catheter ablation procedures that are performed worldwide are estimated to be more than 1 million [44]. The realization of the economic benefit of recovering precious metals such as Au, Pt. Ir and Ta from single-use medical products, as presented in this study, may lead to new and innovative sustainable circular management business models in the future.
Table 7. Relative dissolution percentages of noble metals from various waste streams.
Table 7. Relative dissolution percentages of noble metals from various waste streams.
WasteAcidic SolutionMetal% DissolutionRef.
Electrical and electronic equipmentAqua regiaAu, Ta80–100%, 0%[22]
Anode slimeAqua regiaAu100%[35]
Printed circuit boardsAqua regiaAu100%[45]
Spent automotive catalystsHCl/AlCl3/
HNO3
Pt97–98%[46]
Epoxy-coated solid electrolyte tantalum capacitorsHFTa100%[47]
Slags/Mining tailingsHF/H2SO4Ta87%[24]
Medical–technological productsAqua regia
HF/H2SO4
Au, Pt, Ir, Ta>95% in all metalsPresent study

4. Conclusions and Prospects

In this study, it was proved that medical–technological products can be a valuable secondary (alternative) source of noble metals such as Au, Pt, Ir, and Ta. The incineration-landfill processes, being the main management methods currently applied, can be replaced efficiently by the proposed pyrolysis–acid leaching recovery of metals content. Through the initial pyrolysis at 550 °C, alongside disinfection (although this is not part of the presented research), the plastic parts can be completely discarded, and the overall weight of waste can be substantially decreased. Separate streams of the metals of interest were obtained by applying different acidic mixtures and experimental conditions during the following acidic digestion process. The proposed methodology is considered to be highly selective among the metals of interest, since only in the Au dissolution step were some minor Pt concentrations detected in the liquid phase, and the Au recovery reached almost 100%. On the other hand, the resulting streams of noble metals also contain significant concentrations of other metallic impurities (e.g., Fe, Cr, Ni, Ti, etc.) existing in the initial products, so further investigation is needed, and will be aimed at their selective separation and precipitation from the liquid phase. In addition, Pt and Ir should also be further selectively separated to be potentially re-utilized in other applications.
The results obtained here, however limited, could be seen as a basis for a follow-up pilot study where the technoeconomic analysis of the process could be studied to acquire an idea of a full-scale industrial application of the process. All the products and by-products, such as metal mixtures, solid residue, and acid leachates, can be useful, which makes the reported process eco-friendly in its utilization of single-use medical products as a resource rather than discarding them as waste material.

Author Contributions

Conceptualization, E.K.. and A.Z.; methodology, E.K. and C.P.; software, K.S.; validation, E.K., G.V. and A.Z.; formal analysis, E.P.; investigation, E.K. and A.L.; resources, A.Z.; data curation, E.K., K.S. and A.L.; writing—original draft preparation, E.K. and C.P.; writing—review and editing, E.K., E.P. and A.Z.; visualization, E.K. and K.S.; supervision, G.V. and A.Z.; project administration, E.P.; funding acquisition, A.Z. All authors have read and agreed to the published version of the manuscript.

Funding

The project «Collection, processing and metallurgical recovery of critical raw materials (Au, Pt, Ir, Ta) from discarded medical material» (Project code: ΚΜΡ6-0084436) was implemented under the framework of the Action «Investment Plans of Innovation» of the Operational Program «Central Macedonia 2014–2020» that is co-funded by the European Regional Development Fund and Greece.

Data Availability Statement

Data are contained within the article.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Ranjbari, M.; Shams Esfandabadi, Z.; Shevchenko, T.; Chassagnon-Haned, N.; Peng, W.; Tabatabaei, M.; Aghbashlo, M. Mapping healthcare waste management research: Past evolution, current challenges, and future perspectives towards a circular economy transition. J. Hazard. Mater. 2022, 422, 126724. [Google Scholar] [CrossRef] [PubMed]
  2. Kapoor, A.; Vora, A.; Nataraj, G.; Mishra, S.; Kerkar, P.; Manjunath, C.N. Guidance on reuse of cardio-vascular catheters and devices in India: A consensus document. Indian Heart J. 2017, 69, 357–363. [Google Scholar] [CrossRef] [PubMed]
  3. Attrah, M.; Elmanadely, A.; Akter, D.; Rene, E.R. A Review on Medical Waste Management: Treatment, Recycling, and Disposal Options. Environments 2022, 9, 146. [Google Scholar] [CrossRef]
  4. Kane, G.M.; Bakker, C.A.; Balkenende, A.R. Towards design strategies for circular medical products. Resour. Conserv. Recycl. 2018, 135, 38–47. [Google Scholar] [CrossRef]
  5. Niinomi, M. Metals for Biomedical Devices, 2nd ed.; Woodhead Publishing: Duxford, UK, 2019; pp. 1–188. [Google Scholar]
  6. Cowley, A.; Woodward, B. A Healthy Future: Platinum in Medical Applications. Platin. Met. Rev. 2011, 55, 98–107. [Google Scholar] [CrossRef]
  7. Nzulumike, A.N.O.; Thormann, E. Fibrin Adsorption on Cardiovascular Biomaterials and Medical Devices. ACS Appl. Bio Mater. 2022, 6, 2667–2676. [Google Scholar] [CrossRef]
  8. Park, J.S.; Yim, K.H.; Jeong, S.; Lee, D.H.; Kim, D.G. A novel high-visibility radiopaque tantalum marker for biliary self-expandable metal stents. Gut Liver 2019, 13, 366–372. [Google Scholar] [CrossRef]
  9. Zupanc, A.; Install, J.; Jereb, M.; Repo, T. Sustainable and Selective Modern Methods of Noble Metal Recycling. Angew. Chem. —Int. Ed. 2023, 62, e2022144. [Google Scholar] [CrossRef]
  10. Granados-Fernández, R.; Montiel, M.A.; Díaz-Abad, S.; Rodrigo, M.A.; Lobato, J. Platinum recovery techniques for a circular economy. Catalysts 2021, 11, 937. [Google Scholar] [CrossRef]
  11. Fan, C.; Quan, K.; Han, Z.; Han, F.; Li, Z.; Liu, J.; Liu, X. Recovery and Purification of Iridium from Secondary Resources: A Review. J. Sustain. Metall. 2023, 9, 909–926. [Google Scholar] [CrossRef]
  12. Charles, V.; Anumah, A.O.; Adegoke, K.A.; Adesina, M.O.; Ebuka, I.P.; Gaya, N.A.; Ogwuche, S.; Yakubu, M.O. Progress and challenges pertaining to the earthly-abundant electrocatalytic materials for oxygen evolution reaction. Sustain. Mater. Technol. 2021, 28, e00252. [Google Scholar] [CrossRef]
  13. Li, Y.; Zhou, L.; Guo, S. Noble metal-free electrocatalytic materials for water splitting in alkaline electrolyte. EnergyChem 2021, 3, 100053. [Google Scholar] [CrossRef]
  14. Xing, W.D.; Sohn, S.H.; Lee, M.S. A Review on the Recovery of Noble Metals from Anode Slimes. Miner. Process. Extr. Metall. Rev. 2020, 2, 130–143. [Google Scholar] [CrossRef]
  15. Padamata, S.K.; Yasinskiy, A.S.; Polyakov, P.V.; Pavlov, E.A.; Varyukhin, D.Y. Recovery of Noble Metals from Spent Catalysts: A Review. Metall. Mater. Trans. B Process Metall. Mater. Process. Sci. 2020, 51B, 2413–2435. [Google Scholar] [CrossRef]
  16. Ding, Y.; Zhang, S.; Liu, B.; Zheng, H.; Chang, C.C.; Ekberg, C. Recovery of precious metals from electronic waste and spent catalysts: A review. Resour. Conserv. Recycl. 2019, 141, 284–298. [Google Scholar] [CrossRef]
  17. Guimarães, R.; Carvalho, J.; Leal, V.; Guerner Dias, A.J. Characterization, treatment proposal and metal recovery in waste of active implantable medical devices. Comun. Geol. 2014, 101, 1011–1014. [Google Scholar]
  18. He, Y.; Hosseinzadeh-Bandbafha, H.; Kiehbadroudinezhad, M.; Peng, W.; Tabatabaei, M.; Aghbashlo, M. Environmental footprint analysis of gold recycling from electronic waste: A comparative life cycle analysis. J. Clean. Prod. 2023, 432, 139675. [Google Scholar] [CrossRef]
  19. Su, G.; Ong, H.C.; Ibrahim, S.; Fattah, I.M.R.; Mofijur, M.; Chong, C.T. Valorisation of medical waste through pyrolysis for a cleaner environment: Progress and challenges. Environ. Pollut. 2021, 279, 116934. [Google Scholar] [CrossRef]
  20. Jadhao, P.R.; Ahmad, E.; Pant, K.K.; Nigam, K.D.P. Environmentally friendly approach for the recovery of metallic fraction from waste printed circuit boards using pyrolysis and ultrasonication. Waste Manag. 2020, 118, 150–160. [Google Scholar] [CrossRef]
  21. Grilli, M.L.; Slobozeanu, A.E.; Larosa, C.; Paneva, D.; Yakoumis, I.; Cherkezova-Zheleva, Z. Platinum Group Metals: Green Recovery from Spent Auto-Catalysts and Reuse in New Catalysts—A Review. Crystals 2023, 13, 550. [Google Scholar] [CrossRef]
  22. Witt, K.; Urbaniak, W.; Kaczorowska, M.A.; Bożejewicz, D. Simultaneous recovery of precious and heavy metal ions from waste electrical and electronic equipment (WEEE) using polymer films containing cyphos IL 101. Polymers 2021, 13, 1454. [Google Scholar] [CrossRef]
  23. Jimenez De Aberasturi, D.; Pinedo, R.; Ruiz De Larramendi, I.; Ruiz De Larramendi, J.I.; Rojo, T. Recovery by hydrometallurgical extraction of the platinum-group metals from car catalytic converters. Miner. Eng. 2011, 24, 505–513. [Google Scholar] [CrossRef]
  24. Rodríguez, O.; Alguacil, F.J.; Baquero, E.E.; García-Díaz, I.; Fernández, P.; Sotillo, B.; López, F.A. Recovery of niobium and tantalum by solvent extraction from Sn-Ta-Nb mining tailings. RSC Adv. 2020, 10, 21406–21412. [Google Scholar] [CrossRef]
  25. Kokkinos, E.; Merachtsaki, D.; Lampou, A.; Prochaska, C.; Peleka, E.; Simeonidis, K.; Vourlias, G.; Zouboulis, A. Investigating the Recovery of Noble Metals from Single-Use Medical Technology-Specific Waste Streams. Mater. Proc. 2023, 15, 27. [Google Scholar] [CrossRef]
  26. Romanchenko, A.; Likhatski, M.; Mikhlin, Y. X-ray photoelectron spectroscopy (XPS) study of the products formed on sulfide minerals upon the interaction with aqueous platinum (IV) chloride complexes. Minerals 2018, 8, 578. [Google Scholar] [CrossRef]
  27. Pfeifer, V.; Jones, T.E.; Velasco Vélez, J.J.; Arrigo, R.; Piccinin, S.; Hävecker, M.; Knop-Gericke, A.; Schlögl, R. In situ observation of reactive oxygen species forming on oxygen-evolving iridium surfaces. Chem. Sci. 2017, 8, 2143–2149. [Google Scholar] [CrossRef] [PubMed]
  28. Hepperle, P.; Herman, A.; Khanbabaee, B.; Baek, W.Y.; Nettelbeck, H.; Rabus, H. XPS Examination of the Chemical Composition of PEGMUA-Coated Gold Nanoparticles. Part. Part. Syst. Charact. 2022, 39, 2200070. [Google Scholar] [CrossRef]
  29. Simpson, R.; White, R.G.; Watts, J.F.; Baker, M.A. XPS investigation of monatomic and cluster argon ion sputtering of tantalum pentoxide. Appl. Surf. Sci. 2017, 405, 79–87. [Google Scholar] [CrossRef]
  30. Peng, W.; Zeng, W.; Zhang, Y.; Shi, C.; Quan, B.; Wu, J. The effect of colored titanium oxides on the color change on the surface of Ti-5Al-5Mo-5V-1Cr-1Fe alloy. J. Mater. Eng. Perform. 2013, 22, 2588–2593. [Google Scholar] [CrossRef]
  31. Lee, S.H.; Lee, H.; Cho, M.; Lee, Y. A layered hollow sphere architecture of iridium-decorated carbon electrode for oxygen evolution catalysis. Carbon N. Y. 2017, 115, 50–58. [Google Scholar] [CrossRef]
  32. Kolosov, V.N.; Miroshnichenko, M.N. On the Synthesis of Tantalum-Carbide Powder by the Reaction of Tantalum with Toluene. Nanobiotechnol. Rep. 2022, 17, 507–513. [Google Scholar] [CrossRef]
  33. Rao, M.D.; Singh, K.K.; Morrison, C.A.; Love, J.B. Challenges and opportunities in the recovery of gold from electronic waste. RSC Adv. 2020, 10, 4300–4309. [Google Scholar] [CrossRef] [PubMed]
  34. Hojo, M.; Iwasaki, S.; Okamura, K. Pure gold dissolution with hydrogen peroxide as the oxidizer in HBr or HI solution. J. Mol. Liq. 2017, 246, 372–378. [Google Scholar] [CrossRef]
  35. Xing, W.D.; Lee, M.S. Leaching of gold and silver from anode slime with a mixture of hydrochloric acid and oxidizing agents. Geosyst. Eng. 2017, 20, 216–223. [Google Scholar] [CrossRef]
  36. Niemelä, M.; Pitkäaho, S.; Ojala, S.; Keiski, R.L.; Perämäki, P. Microwave-assisted aqua regia digestion for determining platinum, palladium, rhodium and lead in catalyst materials. Microchem. J. 2012, 101, 75–79. [Google Scholar] [CrossRef]
  37. Schreier, G.; Edtmaier, C. Separation of Ir, Pd and Rh from secondary Pt scrap by precipitation and calcination. Hydrometallurgy 2003, 68, 69–75. [Google Scholar] [CrossRef]
  38. Yakoumis, I.; Panou, M.; Moschovi, A.M.; Panias, D. Recovery of platinum group metals from spent automotive catalysts: A review. Clean. Eng. Technol. 2021, 3, 100112. [Google Scholar] [CrossRef]
  39. Syed, S. Recovery of gold from secondary sources-A review. Hydrometallurgy 2012, 115–116, 30–51. [Google Scholar] [CrossRef]
  40. Agulyansky, A. Chemistry of Tantalum and Niobium Fluoride Compounds, 1st ed.; Elsevier: Amsterdam, The Netherlands, 2004; ISBN 9780080529028. [Google Scholar]
  41. Shikika, A.; Sethurajan, M.; Muvundja, F.; Mugumaoderha, M.C.; Gaydardzhiev, S. A review on extractive metallurgy of tantalum and niobium. Hydrometallurgy 2020, 198, 105496. [Google Scholar] [CrossRef]
  42. Dong, H.; Zhao, J.; Chen, J.; Wu, Y.; Li, B. Recovery of platinum group metals from spent catalysts: A review. Int. J. Miner. Process. 2015, 145, 108–113. [Google Scholar] [CrossRef]
  43. He, Y.; Kiehbadroudinezhad, M.; Hosseinzadeh-Bandbafha, H.; Gupta, V.K.; Peng, W.; Lam, S.S.; Tabatabaei, M.; Aghbashlo, M. Driving sustainable circular economy in electronics: A comprehensive review on environmental life cycle assessment of e-waste recycling. Environ Pollut. 2023, 342, 123081. [Google Scholar] [CrossRef] [PubMed]
  44. Worldwide Cardiac Ablation Catheters Industry to 2025—US Is Expected to Experience the Most Rapid Growth. Available online: https://www.globenewswire.com/news-release/2021/07/13/2261690/28124/en/Worldwide-Cardiac-Ablation-Catheters-Industry-to-2025-US-is-Expected-to-Experience-the-Most-Rapid-Growth.html (accessed on 28 December 2023).
  45. Vlasopoulos, D.; Mendrinou, P.; Oustadakis, P.; Kousi, P.; Stergiou, A.; Karamoutsos, S.D.; Hatzikioseyian, A.; Tsakiridis, P.E.; Remoundaki, E.; Agatzini-Leonardou, S. Hydrometallurgical recovery of silver and gold from waste printed circuit boards and treatment of the wastewater in a biofilm reactor: An integrated pilot application. J. Environ. Manag. 2023, 344, 118334. [Google Scholar] [CrossRef] [PubMed]
  46. Rzelewska, M.; Regel-Rosocka, M. Wastes generated by automotive industry—Spent automotive catalysts. Phys. Sci. Rev. 2019, 3, 20180021. [Google Scholar] [CrossRef]
  47. Chen, W.S.; Ho, H.J.; Lin, K.Y. Hydrometallurgical process for tantalum recovery from epoxy-coated solid electrolyte tantalum capacitors. Materials 2019, 12, 1220. [Google Scholar] [CrossRef]
Figure 1. Medical–technological products examined as reference materials in this study: (a) diagnostic electrophysiology catheter; (b) diagnostic guide wire; and (c) self-expanding stent.
Figure 1. Medical–technological products examined as reference materials in this study: (a) diagnostic electrophysiology catheter; (b) diagnostic guide wire; and (c) self-expanding stent.
Minerals 14 00090 g001
Figure 2. Noble metals’ XPS diagrams of the initial and pyrolyzed samples: (ad) catheter; (e,f) guide wire; and (g,h) stent (each color represents a peak that was obtained in high resolution core-level spectra).
Figure 2. Noble metals’ XPS diagrams of the initial and pyrolyzed samples: (ad) catheter; (e,f) guide wire; and (g,h) stent (each color represents a peak that was obtained in high resolution core-level spectra).
Minerals 14 00090 g002
Figure 3. SEM images of initial and pyrolyzed samples; diagnostic catheter (a) before and (b) after pyrolysis; guide wire (c) before and (d) after pyrolysis; stent (e) before and (f) after pyrolysis.
Figure 3. SEM images of initial and pyrolyzed samples; diagnostic catheter (a) before and (b) after pyrolysis; guide wire (c) before and (d) after pyrolysis; stent (e) before and (f) after pyrolysis.
Minerals 14 00090 g003aMinerals 14 00090 g003b
Table 1. Dissolution of noble metals in various case studies.
Table 1. Dissolution of noble metals in various case studies.
ReagentWaste TypeMetals of InterestOther Metals Ref.
AuPtIrTa
Aqua regiaElectrical and electronic equipment---Ni, Co, Fe[22]
HCl/H2O2Anode slimes--Pd, Cu[14]
Aqua regiaSpent catalysts--Pd, Rh[23]
Aqua regiaSpent catalysts--Pd, Rh[15]
HF/H2SO4Slags/Mining tailings---Nb[24]
Aqua regia and
HF/H2SO4
Medical–technological productsFe, Cr, Ni, TiPresent study
✓: The symbol indicates the metals under investigation.
Table 2. EDS analysis on specific areas of samples containing the noble metals.
Table 2. EDS analysis on specific areas of samples containing the noble metals.
Medical ProductSpecific AreaPtIrAuTaO
wt%
Diagnostic catheterPt/Ir marker band77.6 ± 4.78.3 ± 1.6--14.1 ± 3.2
Guide-wireAu-coated guide wire--86.6 ± 5.4-11.3 ± 2.7
Self-expanding stentTa marker dot---81.9 ± 4.818.1 ± 3.8
Table 3. Results of pyrolysis experiments (conditions: 550 °C for 60 min).
Table 3. Results of pyrolysis experiments (conditions: 550 °C for 60 min).
Medical ProductSolid Residue (wt%)Mass Loss (wt%)
Guide wire, metal of interest: Au
Plastic part/Metallic part
1.06/10098.9/0
Diagnostic catheter,
metals of interest: Pt/Ir
46.3653.6
Self-expanding stent,
metal of interest: Τa
93.07.0
Table 4. EDS analysis at specific areas of pyrolyzed samples containing the noble metals.
Table 4. EDS analysis at specific areas of pyrolyzed samples containing the noble metals.
Medical ProductSpecific AreaPtIrAuTaO
wt%
Diagnostic catheterPt/Ir marker band74 ± 4.57.5 ± 0.4--15.9 ± 2.6
Guide-wireAu-coated guide wire--89.9 ± 1.2-7.4 ± 1.4
Self-expanding stentTa marker dot---71.2 ± 5.124.7 ± 4.8
Table 5. Acid digestion of the samples, aiming for Au separation. Conditions: 30 min, no heating.
Table 5. Acid digestion of the samples, aiming for Au separation. Conditions: 30 min, no heating.
Acidic SolutionAuPtIrTaFeCrNiTi
(50% v/v)mg/L
HCl62---1143083
HNO342---982152
HCl/H2O2 (3:1)102---156423728
HCl/HNO3 (3:1)208---27081306150
HCl/HNO3-concentrated2100.8--392115431182
Table 6. Acid digestion conditions of the samples’ residue, aiming for Pt, Ir, and Ta separation.
Table 6. Acid digestion conditions of the samples’ residue, aiming for Pt, Ir, and Ta separation.
Acidic SolutionMaterialTTimePtIrTaFeCrNiTi
°Chmg/L
HCl/HNO3-concentratedAu digestion residue250.50.8--392115431182
HCl/HNO3-concentratedAu digestion residue904844943.6558420215871372
HCl/HNO3-concentratedAu digestion residue907265361858720016721411
HF 50% v/vPt/Ir digestion residue9010--38----
HF/H2SO4 50% v/vPt/Ir digestion residue9010--175----
HF/H2SO4 50% v/vPt/Ir marker band90721630-----
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Kokkinos, E.; Prochaska, C.; Lampou, A.; Peleka, E.; Simeonidis, K.; Vourlias, G.; Zouboulis, A. Recovery of Noble Metals (Au, Pt, Ir, and Ta) from Spent Single-Use Medical–Technological Products. Minerals 2024, 14, 90. https://doi.org/10.3390/min14010090

AMA Style

Kokkinos E, Prochaska C, Lampou A, Peleka E, Simeonidis K, Vourlias G, Zouboulis A. Recovery of Noble Metals (Au, Pt, Ir, and Ta) from Spent Single-Use Medical–Technological Products. Minerals. 2024; 14(1):90. https://doi.org/10.3390/min14010090

Chicago/Turabian Style

Kokkinos, Evgenios, Charikleia Prochaska, Angeliki Lampou, Effrosyni Peleka, Konstantinos Simeonidis, Georgios Vourlias, and Anastasios Zouboulis. 2024. "Recovery of Noble Metals (Au, Pt, Ir, and Ta) from Spent Single-Use Medical–Technological Products" Minerals 14, no. 1: 90. https://doi.org/10.3390/min14010090

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