CoChat
Sign Up
Cited by 10Mine drainage and remediation techniquesMetal Extraction and BioleachingExtraction and Separation Processes

Metallic Copper (Cu[0]) Obtained from Cu2+-Rich Acidic Mine Waters by Two Different Reduction Methods: Crystallographic and Geochemical Aspects

Open access
Sánchez-España, Javier, Ilin, Andrey, Yusta, Iñaki·2022·Minerals
DOI 10.3390/min12030322
Open this paper in CoChat — free accountOpen PDF

Abstract

The recovery of valuable metals from different types of wastes has become of prime strategic interest given the scarcity of primary critical raw materials at international scale. Implementation of new methods or refinement of classical techniques with modern technological advances is, therefore, an active research field. Mine wastes are of special interest because their high metal concentrations make them environmentally harmful and economically profitable at the same time. In this study, we evaluated two different methods of Cu recovery from extremely acidic mine waters seeping from wastes and abandoned mines in SW Spain. Through a series of different batch experiments, we compared the method efficiency and crystallographic properties of elemental copper (Cu[0]) obtained by reduction of Cu2+ ions by (1) chemical reduction using ascorbic acid at different environmental conditions of pH (1.50–3.95), temperature (25–80 °C) and ascorbic acid concentration (10 mM to 0.1 M), and (2) classical cementation method with scrap iron at pH 1.50 and 25 °C. Our study demonstrates that the precipitation of Cu[0] can take place at pH 3.95 and low AA concentrations (0.1 M), resulting in large (µm-scale), perfectly developed crystals of copper with pseudoprismatic to acicular habit after 24 h of aging, likely through formation of a transient compound consisting in Cu2+-ascorbate and/or cuprite (Cu2O) nanocolloids. Reduction experiments at higher AA concentrations (0.1 M) showed faster precipitation kinetics and resulted in high-purity (>98%) copper suspensions formed by subrounded nanoparticles. The AA method, however, yielded very low recovery rates (15–25%) because of the low pH values considered. The cementation method, which produced tree-like aggregates formed by sub-micron crystals arranged in different directions, proved to be much more efficient (>98% recovery) and cost-effective.

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Integrity signals

Registry

Crossref · 10.3390/min12030322

Cites

Statistics

Claims the paper makes

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Claims other papers make about this one

Each is checked against this paper’s own text: does it say what the citing paper says it does?

  • The formation of copper deposits requires electron donation from a metallic reducing agent.

    “These findings confirm that the formation of copper deposits requires electron donation from a metallic reducing agent [34], [35], [36], [37].”

    From Identification of the Redox Reaction Between CuSO₄ and Zn Through Visual Observation in Basic Chemistry (2026) · cites this paper as [36]

    Section 4.2 describes copper forming when scrap iron reduces Cu²⁺, but the paper does not say a metallic reducing agent is required. The Introduction and §2.2.1 describe a second method in which nonmetallic ascorbic acid or ascorbate reduces Cu²⁺, contrary to that requirement. (LLM, conf=0.89)

    Checked by a reasoning model — may be wrong.

    Experimental — accuracy not yet measured

Self-check

Percentages, sums and reported differences re-computed from the paper’s own numbers.

The self-check needs the paper’s full text.

Cites

No references could be resolved yet.

Research works printed but not linked: 37

  1. Ghosh, S. Electroless copper deposition: A critical review. Thin Solid Films 2019, 669, 641-658. [CrossRef] · DOI
  2. Saikova, S.V.; Murasheva, K.S.; Vorobyev, S.A.; Kochmarev, K.Y.; Karimov, E.E.; Eremina, A.D.; Mikhlin, Y.L. Synthesizing highly concentrated hydrosols of copper nanoparticles via reduction by ascorbic acid in the presence of gelatose. Chem. Sust. Dev. 2013, 21, 403-409.
  3. Andal, V.; Buvaneswari, G. Effect of reducing agents in the conversion of Cu 2 O nanocolloid to Cu nanocolloid. Eng. Sci. Technol. 2017, 20, 340-344. [CrossRef] · DOI
  4. Kumar, S.; Kumar, V.; Sharma, M.L.; Chakarvarti, S.K. Electrochemical synthesis of metallic micro-rose having petals in nanometer dimensions. Superlattice Microstruct. 2008, 43, 324-329. [CrossRef] · DOI
  5. Tsai, C.-Y.; Chang, W.-C.; Chen, G.-L.; Chung, C.-H.; Liang, J.-X.; Ma, W.-Y. A study of the preparation and properties of antioxidative copper inks with high electrical conductivity. Nanoscale Res. Lett. 2015, 10, 357. [CrossRef] [PubMed] · DOI
  6. Virk, H.S. Fabrication and characterization of metallic copper and copper oxide nanoflowers. Pak. J. Chem. 2011, 1, 148-154. [CrossRef] · DOI
  7. Virk, H.S.; Kishore, K.; Balouria, V. Fabrication of copper nanowires by electrodeposition using anodic alumina and polymer templates. J. Nano Res. 2010, 10, 63-67. [CrossRef] · DOI
  8. Sarkar, J.; Khan, G.G.; Basumallick, A. Nanowires: Properties, applications and synthesis via porous anodic aluminum oxide template. Bull. Mater. Sci. 2007, 30, 271-290. [CrossRef] · DOI
  9. Zhang, D.-F.; Zhang, H.; Guo, L.; Zheng, K.; Han, X.-D.; Zhang, Z. Delicate control of crystallographic facet-oriented Cu 2 O nanocrystals and the correlated adsorption ability. J. Mater. Chem. 2009, 19, 5220-5225. [CrossRef] · DOI
  10. Lottermoser, B.G. Recycling, Reuse and Rehabilitation of Mine Wastes. Elements 2011, 7, 405-410. [CrossRef] · DOI
  11. Plumlee, G.S., Logsdon, M.J., Eds.; Society of Economic Geologists: Littleton, CO, USA, 1999; Volume 6, pp. 133-156.
  12. Geller, W.; Klapper, H.; Schultze, M. Natural and anthropogenic sulphuric acidification of lakes. In Acidic Mining Lakes-Acid Mine Drainage, Limnology and Reclamation; Geller, W., Klapper, H., Salomons, W., Eds.; Springer: Berlin/Heidelberg, Germany, 1998; pp. 3-14.
  13. Barthen, R.; Sulonen, M.L.K.; Peräniemi, S.; Jain, R.; Lakaniemi, A.M. Removal and recovery of metal ions from acidic multi-metal mine water using waste digested activated sludge as biosorbent. Hydrometallurgy 2022, 207, 105770. [CrossRef] · DOI
  14. Isosaari, P.; Sillampää, M. Use of Sulfate-Reducing and Bioelectrochemical Reactors for Metal Recovery from Mine Water. Sep. Purif. Rev. 2014, 46, 1-20. [CrossRef] · DOI
  15. León, R.; Macías, F.; Cánovas, C.; Pérez-López, R.; Ayora, C.; Nieto, J.M.; Olías, M. Mine waters as a secondary source of rare earth elements worldwide: The case of the Iberian Pyrite Belt. J. Geochem. Exp. 2021, 224, 106742. [CrossRef] · DOI
  16. Sánchez-España, F.J.; López Pamo, E.; Santofimia, E.; Aduvire, O.; Reyes, J.; Barettino, D. Acid Mine Drainage in the Iberian Pyrite Belt (Odiel river watershed, Huelva, SW Spain): Geochemistry, Mineralogy and Environmental Implications. App. Geochem. 2005, 20, 1320-1356. [CrossRef] · DOI
  17. Sánchez España, J.; López Pamo, E.; Santofimia, E.; Diez-Ercilla, M. The acidic mine pit lakes of the Iberian Pyrite Belt: An approach to their physical limnology and hydrogeochemistry. App. Geochem. 2008, 23, 1260-1287. [CrossRef] · DOI
  18. Sánchez-España, J.; Diez, M.; Santofimia, E. Mine pit lakes of the Iberian Pyrite Belt: Some basic limnological, hydrogeochemical and microbiological considerations. In Acidic Pit Lakes: The Legacy of Coal and Metal Surface Mines; Geler, W., Ed.; Springer: Berlin/Heidelberg, Germany, 2013; pp. 315-342.
  19. Taylor, J.H.; Whelan, P.F. The leaching of cupreous pyrites and the precipitation of copper at Rio Tinto, Spain. Trans. Inst. Min. Metall. 1943, 52, 35-96.
  20. Tucci, N.J.; Gammons, C.H. Influence of copper recovery on the water quality of the acidic Berkeley Pit lake, Montana, U.S.A. Environ. Sci. Technol. 2015, 49, 4081-4088. [CrossRef] · DOI
  21. Bigham, J.M.; Nordstrom, D.K. Iron and Aluminum Hydroxysulfates from Acid Sulfate Waters. In Sulfate Minerals: Crystallogra- phy, Geochemistry, and Environmental Significance. Rev. Mineral. Geochem. 2000, 40, 351-403. [CrossRef] · DOI
  22. Sánchez-España, J. The behavior of iron and aluminum in acid mine drainage: Speciation, mineralogy, and environmental significance. In Thermodynamics, Solubility and Environmental issues; Letcher, T., Ed.; Elsevier: Amsterdam, The Netherlands, 2007; pp. 137-150.
  23. Sánchez-España, J.; López-Pamo, E.; Santofomia, E.; Reyes, J.; Martín-Rubí, J.A. The removal of dissolved metals by hydroxysul- phate precipitates during oxidation and neutralization of acid mine waters, Iberian Pyrite Belt. Aquat. Geochem. 2006, 12, 269-298. [CrossRef] · DOI
  24. Sánchez-España, J.; Yusta, I.; López, G. Schwertmannite to jarosite conversion in the water column of an acidic mine pit lake. Mineral. Mag. 2012, 76, 2659-2682. [CrossRef] · DOI
  25. Nordstrom, D.K. The effect of sulphate on aluminum concentrations in natural waters: Some stability relations in the system Al 2 O 3 -SO 3 -H 2 O at 298 K. Geochim. Cosmochim. Acta 1982, 46, 681-692. [CrossRef] · DOI
  26. Sánchez-España, J.; Yusta, I.; Burgos, W.D. Geochemistry of dissolved aluminum at low pH: Hydrobasaluminite formation and interaction with trace metals, silica and microbial cells under anoxic conditions. Chem. Geol. 2016, 441, 124-137. [CrossRef] · DOI
  27. Shen, J.; Griffiths, P.T.; Campbell, S.J.; Utinger BKalberer, M.; Paulson, S.E. Ascorbate oxidation by iron, copper and reactive oxygen species: Review, model development, and derivation of key rate constants. Sci. Rep. 2021, 11, 7417. [CrossRef] [PubMed] · DOI
  28. Sánchez-España, J.; Yusta, I. Low-crystallinity products of trace-metal precipitation in neutralized pit-lake waters without ferric and aluminous adsorbent: Geochemical modelling and mineralogical analyses. Mineral. Mag. 2015, 79, 781-798. [CrossRef] · DOI
  29. Mystkowski, E.M. The oxidation of ascorbic acid in the presence of copper. Biochem, J. 1942, 36, 494-500. [CrossRef] · DOI
  30. Hacisevkí, A. An overview of ascorbic acid biochemistry. J. Fac. Pharm. Ank. 2009, 38, 233-255.
  31. Goçalves, T.A.; Botelho, A.B.; de Moraes, V.T.; Espinos, D.C.R. Study of pH Influence in the Synthesis of Copper Nanoparticles Using Ascorbic Acid as Reducing and Stabilizing Agent. In Proceedings of the TMS 2020 149th Annual Meeting & Exhibition, San Diego, CA, USA, 23-27 February 2020; The Minerals, Metals & Materials Society, Ed.; The Minerals, Metals & Materials Series; Springer Nature: Cham, Switzerland, 2020; pp. 1547-1557.
  32. Liu, Q.M.; Yasunami, T.; Kuruda, K.; Okido, M. Preparation of Cu nanoparticles with ascorbic acid by aqueous solution reduction method. Trans. Nonferrous Met. Soc. China 2012, 22, 2198-2203. [CrossRef] · DOI
  33. Songping, W. Preparation of fine copper powder using ascorbic acid as reducing agent and its application in MLCC. Mater. Lett. 2017, 61, 1125-1129. [CrossRef] · DOI
  34. Sánchez-España, J. Crystallization in acidic media: From nanoparticles to macrocrystals. Semin. Soc. Esp. Mineral. 2017, 13, 15-34.
  35. Jacukowicz-Sobala, I.; Stanisławska, E.; Baszczuk, A.; Jasiorski, M.; Kociołek-Balawejder, E. Size-Controlled Transformation of Cu 2 O into Zero Valent Copper within the Matrix of Anion Exchangers via Green Chemical Reduction. Polymers 2020, 12, 2629. [CrossRef] · DOI
  36. Ünalero glu, C.; Mert, Y.; Zümreo glu-Karan, B. Synthesis and characterization of copper ascorbate. Synth. React. Inorg. Met.-Org. Chem. 2001, 31, 1531-1543. [CrossRef] · DOI
  37. Stefanowicz, T.; Osinska, M.; Napieralska-Zagozda, S. Copper recovery by the cementation method. Hydrometallurgy 1997, 47, 69-90. [CrossRef · DOI

Cited by

Sorted by citations

Authors
Sánchez-España, J., Ilin, A., & Yusta, I.
Affiliations
  • Mine Waste and Environmental Geochemistry Research Group, Department of Geological Resources (IGME-CSIC), Calera 1, Tres Cantos, 28760 Madrid, Spain
  • University of the Basque Country (ES)
ORCID
Venue
Minerals
Publisher
MDPI AG
Published
2022-03-04
Volume
12
Issue
3
Pages
322
ISSN
2075-163X (ISSN-L)
DOI
10.3390/min12030322
OpenAlex
W4220870054
Cited by
10
References
0
Citations by year
2025: 5 · 2024: 3 · 2023: 2
FWCI
0.89
Type
journal article
Language
en
Open access
Licence
Locations
  • Minerals (publishedVersion, cc-by)
  • Communities in ADDI (University of the Basque Country) (submittedVersion, cc-by)
  • Hispana (submittedVersion, cc-by)
Funders
Spanish Ministry of Science and Innovation (CGL2016-74984-R)
Topics
  • Physical Sciences › Environmental Science › Environmental Chemistry › Mine drainage and remediation techniques
  • Physical Sciences › Engineering › Biomedical Engineering › Metal Extraction and Bioleaching
  • Physical Sciences › Engineering › Mechanical Engineering › Extraction and Separation Processes
Keywords
copper recovery, copper, acidic mine water, mining waste, ascorbic acid reduction, chemical reduction, cementation, scrap iron, copper nanoparticles, precipitation kinetics, critical raw materials, abandoned mines

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Statistics and arithmetic are recomputed, not judged.

Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.

What counts as a claim ›How we measure confidence ›How we check this ›

Are you an author, or do you see a problem with this page? Request a review