DOI https://doi.org/10.36487/ACG_repo/2415_31
Cite As:
De Oliveira, VH, Duddigan, S, Symons, J, Whelan, MJ, Selvaraj, V, Abbott, AP, Jenkin, GRT & Tibbett, M 2024, 'Can deep eutectic solvents be used to mobilise copper from tailings while providing a pathway towards rehabilitation?', in AB Fourie, M Tibbett & G Boggs (eds),
Mine Closure 2024: Proceedings of the 17th International Conference on Mine Closure, Australian Centre for Geomechanics, Perth, pp. 427-440,
https://doi.org/10.36487/ACG_repo/2415_31
Abstract:
The use of deep eutectic solvents (DESs) has been proposed as a novel technique for environmentally benign mineral processing, with utility in the reprocessing of legacy tailings in a process known as solvometallurgy. These solvents can leach a wide range of metals while having many advantages, such as low volatility, high target metal selectivity, lower production costs and potentially low ecotoxicity. We aimed to determine the capacity of different DESs to mobilise copper (Cu) and other metals from Cu mine tailings. They were: DES 1 (oxaline) – choline chloride + oxalic acid; DES 2 (ethaline) – choline chloride + ethylene glycol; DES 3 – betaine + acetic acid; and DES 4 – betaine + acetic acid + phosphoric acid. In a follow-up experiment, Plantago lanceolata seedlings were transplanted to the tailings after DES application in order to determine phytotoxic responses. Our results showed that Cu extraction from tailings increases with DES concentration and pointed to DES 3 and 4 (betaine-based) as more efficient in Cu leaching, although oxaline was more capable of enhancing nutrient availability. Almost all plants died 24 hours after transplanting to DES-treated tailings, except the ones treated with oxaline, which is possibly linked to the remarkable macronutrient mobilisation – an element known to alleviate Cu phytotoxicity. However, only the diluted oxaline (1:128, DES:water) was able to improve plant growth in tailings as it mobilised more nutrients, leading to greater plant biomass and chlorophyll content. Thus it is clear that hazardous effects will depend on the DES formulation, concentration and exposure route, which may promote extreme phytotoxicity by enhancing metal availability in mine tailings. Yet diluted oxaline showed promising beneficial effects in plant health and growth, indicating that some diluted DESs, at concentrations anticipated after application and leaching, may have a role in promoting land rehabilitation.
Keywords: DES, ecotoxicity, heavy metals, solvometallurgy, phytotoxicity, ecosystem reconstruction, solvent leaching, tailings reprocessing, mine closure
References:
Abbott, AP, Capper, G, Davies, DL, Rasheed, RK & Tambyrajah, V 2003, ‘Novel solvent properties of choline chloride/urea mixtures’, Chemical Communications, no. 1, pp. 70–71.
Abbott, AP, Harris, RC, Holyoak, F, Frisch, G, Hartley, J & Jenkins, GRT 2015, ‘Electrocatalytic recovery of elements from complex mixtures using deep eutectic solvents’, Green Chemistry, vol. 17, no. 4, pp. 2085–2094,
Abranches, DO & Coutinho, JAP 2022, ‘Type V deep eutectic solvents: design and applications’, Current Opinion in Green and Sustainable Chemistry, pp. 100612,
Adiansyah, JS, Rosano, M, Vink, S & Keir, G 2015, ‘A framework for a sustainable approach to mine tailings management: disposal strategies’, Journal of Cleaner Production, vol. 108, pp. 1053–1063,
Ahmed, N, Habib, U, Younis, U, Irshad, I, Danish, S, Subhan, R, Ahmad, AA & Munir, TM 2020, ‘Growth, chlorophyll content and productivity responses of maize to magnesium sulphate application in calcareouis soil’, Open Agriculture, vol. 5, no. 1, pp. 792–800,
Alloway, BJ 2013, ‘Sources of heavy metals and metalloids in soils’, in BJ Alloway (ed.), Heavy Metals in Soils, Springer, Dordrecht, pp. 11–50,
Almeida, J, Craveiro, R, Faria, P, Silva, AS, Mateus, EP, Barreiros, S, Paiva, A & Ribeiro, AB 2020, ‘Electrodialytic removal of tungsten and arsenic from secondary mine resources — deep eutectic solvents enhancement’, Science of The Total Environment, vol. 710, 136364.
Anggara, S, Bevan, F, Harris, RC, Hartley, JM, Frisch, G, Jenkin, GRT & Abbott, AP 2019, ‘Direct extraction of copper from copper sulfide minerals using deep eutectic solvents’, Green Chemistry, vol. 21, pp. 6502–6509,
Aragón-Tobar, CF, Endara, D & de la Torre, E 2024, ‘Dissolution of metals (Cu, Fe, Pb, and Zn) from different metal-bearing species (sulfides, oxides, and sulfates) using three deep eutectic solvents based on choline chloride’, Molecules, vol. 29, pp. 1–15,
Arrachart, G, Couturier, J, Dourdain, S, Levard, C & Pellet-Rostaing, S 2021, ‘Recovery of rare earth elements (REEs) using ionic solvents’, Processes, vol. 9, no. 7,
Binnemans, K & Jones, PT 2017, ‘Solvometallurgy: an emerging branch of extractive metallurgy’, Journal of Sustainable Metallurgy, vol. 3, pp. 570–600,
Cardellini, F, Germani, R, Cardinali, G, Corte, L, Roscini, L, Spreti, N & Tiecco, M 2015, ‘Room temperature deep eutectic solvents of (1S)-(+)-10-camphorsulfonic acid and sulfobetaines: hydrogen bond-based mixtures with low ionicity and structuredependent toxicity’, RSC Advances, vol. 5, pp. 31772–31786,
Chen, BC, Ho, PC & Juang, KW 2013, ‘Alleviation effects of magnesium on copper toxicity and accumulation in grapevine roots evaluated with biotic ligand models’, Ecotoxicology, vol. 22, pp. 174–183.
Chen, Y & Mu, T 2021, ‘Revisiting greenness of ionic liquids and deep eutectic solvents’, Green Chemical Engineering, pp. 174–186,
de Morais, P, Gonçalves, F, Coutinho, JAP & Ventura, SPM 2015, ‘Ecotoxicity of cholinium-based deep eutectic solvents’, ACS Sustainable Chemistry & Engineering, vol. 3, no. 12, pp. 3398–3404,
De Oliveira, VH, Mazzafera, P & López de Andrade, SA 2022, ‘Alleviation of low phosphorus stress in Eucalyptus grandis by arbuscular mycorrhizal symbiosis and excess Mn’, Plant Stress, vol. 5, 100104,
Degani, E, Warr, B & Tibbett, M 2022, ‘Can Pongamia pinnata be an effective phytoremediation tool for tailings in the Copperbelt of Zambia?’, in AB Fourie, M Tibbett & G Boggs (eds), Mine Closure 2022: Proceedings of the 15th International Conference on Mine Closure, Australian Centre for Geomechanics, Perth, pp. 357–366,
Dlugosz, O, Krawczyk, P & Banach, M 2024, ‘Equilibrium, kinetics and thermodynamics of metal oxide dissolution based on CuO in a natural deep eutectic solvent’, Chemical Engineering Research and Design, vol. 202, pp. 365–376,
Drogobuzhskaya, S, Frolova, M, Shishov, A & Tsvetov, N 2024, ‘Comparison of extraction abilities of deep eutectic solvents and aqueous acid solutions for extraction of rare earths and transition metals’, Journal of Rare Earths, vol. 42, issue 6,
Ferreira, IJ, Oliveira, F, Jesus, AR, Paiva, A & Duarte, ARC 2022, ‘Current methodologies for the assessment of deep eutectic systems toxicology: challenges and perspectives’, Journal of Molecular Liquids, vol. 362, 119675,
j.molliq.2022.119675
Gaustad, G, Williams, E & Leader, A 2021, ‘Rare earth metals from secondary sources: review of potential supply from waste and byproducts’, Resources, Conservation and Recycling, vol. 167, 105213,
Hawkesford, MJ, Cakmak, I, Coskun, D, De Kok, LJ, Lambers, H, Schjoerring, JK & White, PJ 2023, ‘Functions of macronutrients’,
in Z Rengel, I Cakmak & PJ White (eds), Marschner’s Mineral Nutrition of Plants, Academic Press, London, pp. 201–281,
Hayyan, M, Hashim, MA, Hayyan, A, Al-Saadi, MA, AlNashef, IM, Mirghani, MES & Saheed, OK 2013, ‘Are deep eutectic solvents benign or toxic?’, Chemosphere, vol. 90, issue 7, pp. 2193–2195,
Hayyan, M, Looi, CY, Hayyan, A, Wong, WF & Hashim, MA 2015, ‘In vitro and in vivo toxicity profiling of ammonium-based deep eutectic solvents’, PLoS ONE, vol. 10, no. 2, e0117934,
Jenkin, GRT, Al-Bassam, AZM, Harris, RC, Abbott, AP, Smith, DJ, Holwell, DA, Chapman, RJ & Stanley, CJ 2016, ‘The application of deep eutectic solvent ionic liquids for environmentally-friendly dissolution and recovery of precious metals’, Minerals Engineering, vol. 87, pp. 18–24,
Jenkin, GRT, Arcilla, CA, Abbott, AA, Bateson, L, Bautista VII, AT, Chambers, … Yan, Y 2024, ‘Recent developments in the science and technology of in situ solvent leaching of tailings for reprocessing, rehabilitation and closure’, in AB Fourie, M Tibbett
& G Boggs (eds), Mine Closure 2024: Proceedings of the 16th International Conference on Mine Closure, Australian Centre for Geomechanics, Perth, pp. 29–44.
Juang, KW, Lo, YJ & Chen, BC 2021, ‘Modeling alleviative effects of Ca, Mg, and K on Cu-induced oxidative stress in grapevine roots grown hydroponically’, Molecules, vol. 26, no. 17, article 5356,
Khan, AS, Sakina, Nasrullah, A, Ullah, S, Ullah, Z, Khan, Z, Khan, NA, Khan, SZ & Din, IU 2023, ‘An overview on phytotoxic perspective of ionic liquids and deep eutectic solvents: the role of chemical structure in the phytotoxicity’, ChemBioEng Reviews, vol. 10, no. 2, pp. 174–194.
Khandelwal, S, Tailor, YK & Kumar, M 2016, ‘Deep eutectic solvents (DESs) as eco-friendly and sustainable solvent/catalyst systems in organic transformations’, Journal of Molecular Liquids, vol. 215, pp. 345–386,
Kudlak, B, Owczarek, K & Namieśnik, J 2015, ‘Selected issues related to the toxicity of ionic liquids and deep eutectic solvents—a review’, Environmental Science and Pollution Research, vol. 22, pp. 11975–11992,
Kumar, V, Pandita, S, Sidhu, GPS, Sharma, A, Khanna, K, Kaur, P, Bali, AS & Setia, R 2021, ‘Copper bioavailability, uptake, toxicity and tolerance in plants: a comprehensive review’, Chemosphere, vol. 262, 127810,
.
2020.127810
Lapeña, D, Errazquin, D, Lomba, L, Lafuente, C & Giner, B 2021, ‘Ecotoxicity and biodegradability of pure and aqueous mixtures of deep eutectic solvents: glyceline, ethaline, and reline’, Environmental Science and Pollution Research, vol. 28, pp. 8812–8821,
Legendre, P, & Legendre, L 2012, ‘Ordination in reduced space’, Developments in Environmental Modelling, pp. 425–520,
Li, D 2022, ‘Natural deep eutectic solvents in phytonutrient extraction and other applications’, Frontiers in Plant Science, vol. 13, article 1004332,
Li, K, Lu, H, Nkoh Nkoh, J, Hong, Z, & Xu R 2022, ‘Aluminum mobilization as influenced by soil organic matter during soil and mineral acidification: A constant pH study’, Geogerma, pp. 115853,
Liu, H, Lv, J, & Yang, Y 2024, ‘Recyclable water-modified deep eutectic solvents for removal of multiple heavy metals from soil’, Chemosphere, pp. 141141,
Macário, IPE, Jesus, F, Pereira, JL, Ventura, SPM, Gonçalves, AMM, Coutinho, JAP & Gonçalves, FJM 2018, ‘Unraveling the ecotoxicity of deep eutectic solvents using the mixture toxicity theory’, Chemosphere, vol. 212, pp. 890–897,
j.chemosphere.2018.08.153
Martínez Martínez, G, Guillena Townley, G & Martínez-Espinosa, RM 2022, ‘Controversy on the toxic nature of deep eutectic solvents and their potential contribution to environmental pollution’, Heliyon, vol. 8, issue 12, article e12567,
j.heliyon.2022.e12567
Ngole-Jeme, VM & Fantke, P 2017, ‘Ecological and human health risks associated with abandoned gold mine tailings contaminated soil’, PLoS ONE, vol. 12, no. 2, e0172517,
Patelli, IM, Thompson, D, Al Abdullah, SEM, Abbott, AP, Jenkin, GRT & Hartley, JR 2020, ‘The effect of pH and hydrogen bond donor on the dissolution of metal oxides in deep eutectic solvents’, Green Chemistry, vol. 22, pp. 5476–5486,
Radošević, K, Cvjetko Bubalo, M, Gaurina Srček, V, Grgas, D, Landeka Dragičević, T & Radojčić Redovniković, I 2015, ‘Evaluation of toxicity and biodegradability of choline chloride based deep eutectic solvents’, Ecotoxicology and Environmental Safety, vol. 112, pp. 46–53,
Rengel, ZA, Bose, JB, Chen, QC, & Tripathi, BND 2015, ‘Magnesium alleviates plant toxicity of aluminium and heavy metals’, Crop and Pasture Science, vol. 66, no. 12, pp. 1298–1307,
Rodrigues, LA, Cardeira, M, Leonardo, IC, Gaspar, FB, Radojčić Redovniković, I, Duarte, ARC, Paiva, A & Matias, AA 2021, ‘Deep eutectic systems from betaine and polyols – ohysicochemical and toxicological properties’, Journal of Molecular Liquids, vol. 335, 116201,
Rodriguez Rodriguez, N, Machiels, L, & Binnemans, K 2019a, 'p-Toluenesulfonic Acid-Based Deep-Eutectic Solvents for Solubilizing Metal Oxides’, ACS Sustainable Chemistry & Engineering, vol. 7, no. 4, pp. 3940-3948. DOI: 10.1021/acssuschemeng.8b05072
Rodriguez Rodriguez, N, Machiels, L, Onghena, B, Spooren, J & Binnemans, K 2020, ‘Selective recovery of zinc from goethite residue in the zinc industry using deep-eutectic solvents’, RSC Advances, vol. 10, pp. 7328.
Rodriguez Rodriguez, N, van den Bruinhorst, A, Kollau, LJB, Kroon, MC, & Binnemans, K 2019b, ‘Degradation of deep-eutectic solvents based on choline chloride and carboxylic acids’, Sustainable Chemistry & Engineering, vol. 7, no. 13, pp. 11521–11528,
Samori, C, Mazzei, L, Ciurli, S, Cravotto, G, Grillo, G, Guidi, E, Pasteris, A, Tabasso, S, & Galletti, P 2019, ‘Urease inhibitory potential and soil ecotoxicity of novel “polyphenols–deep eutectic solvents” formulations’, ACS Sustainable Chemistry & Engineering, vol. 7, no. 18, pp. 15558–15567,
Shacklette, H, & Boerngen, J 1984, Element Concentrations in Soils and Other Surficial Materials of the Conterminous United States, US Geological Survey Professional Paper 1270, United States Government Printing Office, Washington.
Smith, EL, Abbott, AP, Ryder, KS 2014, ‘Deep eutectic solvents (DESs) and their application’, Chemical Reviews, pp. 11060–11082,
Soltangheisi, A, Hales-Henao, A, Pena, R, & Tibbett, M 2024, ‘Species-specific effects of mycorrhizal symbiosis on Populus trichocarpa after a lethal dose of copper’, Ecotoxicology and Environmental Safety, vol. 272, 116112,
j.ecoenv.2024.116112
Tibbett, M 2024, ‘Post-mining ecosystem reconstruction’, Primer, vol. 34, no. 9, pp. PR387–R393,
j.cub.2024.03.065
Wen, Q, Chen, JX, Tang, YL, Wang, J, & Yang, Z 2015, ‘Assessing the toxicity and biodegradability of deep eutectic solvents’, Chemosphere, vol. 132, pp. 63–69,
Xu, DM, Zhan, CL, Liu, HX, & Lin, HZ 2019, ‘A critical review on environmental implications, recycling strategies, and ecological remediation for mine tailings’, Environmental Science and Pollution Research, vol. 26, pp. 35657–35669,