Document Type : Original Research Paper

Authors

1 State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming, Yunnan 650093, PR China

2 State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Yunnan Key Laboratory of Green Separation and Enrichment of Strategic Metal Resources, Faculty of Land Resources Engineering, Kunming University of Science

3 Department of Chemistry, Faculty of Education, University of Nyala, Nyala 63311, Sudan

4 Department of Mining Engineering, Faculty of Engineering Science, Omdurman Islamic University, Khartoum 14411, Sudan

10.22044/jme.2026.17042.3355

Abstract

In this study, Pb²⁺ and STG were used as effective co-activation reagents before sodium sulfide treatment to assess their effect on smithsonite floatability. The flotation test results showed that sodium sulfide nonahydrate (SSN) and sodium diethyl dithiocarbamate (DDTC) concentrations significantly impacted floatability, achieving maximum recoveries of 89.32% and 93.19%, respectively. XPS analysis confirmed that Na₂S treatment introduced sulfur species onto the smithsonite surface, enhancing collector attachment and facilitating the formation of PbS and ZnS. FTIR analysis further substantiated that co-activation enhances DDTC adsorption via C=S vibrations, thereby increasing the number of active sites available for interaction with the collector relative to direct sulfidation. FESEM-EDS and AFM analysis at pH 9 confirmed that co-activation resulted in the formation of denser, cloud-like layers of PbS and ZnS on the surface. These layers improved flotation efficiency, increased hydrophobicity, and strengthened DDTC interaction, thus promoting flotation. Additionally, ToF-SIMS and EPMA analyses indicated higher Pb⁺ and S⁻ intensities in the co-activation system, confirming enhanced surface reactivity and substantiating the increased activity and diversity of sulfidation products. This study offers an effective approach to enhancing smithsonite flotation recovery by optimizing surface chemistry and collector attachment.

Keywords

Main Subjects

[1].          Yang, T., Rao, S., Zhang, D., Wen, J., Liu, W., Chen, L., & Zhang, X. (2016). Leaching of low grade zinc oxide ores in nitrilotriacetic acid solutions. Hydrometallurgy, 161, 107–111.
[2].          Ehsani, A., Ehsani, I., & Obut, A. (2021). Preparation of different zinc compounds from a smithsonite ore through ammonia leaching and subsequent heat treatment. Physicochemical Problems of Mineral Processing, 57, 96–106.
[3]           . Cook, R. (2000). Connoisseur’s Choice: Smithsonite, Tsumeb, Namibia. Rocks & Minerals, 75, 176–179.
[4]           . Ding, W., Chen, Q., Li, Y., & Liu, X. (2023). Origins of Colour of Smithsonite from Yunnan, China. Minerals 13,  296.
[5].          Li, R., Shao, Y., Li, J., Liu, C., Chen, H., Meng, X., & Jia, X. (2024). Mechanism of Efficient Smithsonite Flotation with a Ternary Composite Collector Under Sulfur-Free Conditions. Molecules, 29, 6014.
[6].          Boryczko, B., Hołda, A., & Kolenda, Z. (2014). Depletion of the non-renewable natural resource reserves in copper, zinc, lead and aluminium production. Journal of Cleaner Production, 84,  313–321.
[7]           . Daigo, I., Osako, S., Adachi, Y., & Matsuno, Y. (2014). Time-series analysis of global zinc demand associated with steel. Resources, Conservation and Recycling, 82,  35–40.
[8]           . Chen, Y., Guo, X., & Chen, Y. (2023). Adsorption study of sesbania gum onto calcite surface: Implications for smithsonite-calcite flotation separation. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 676, 132174.
[9]           . Yan, L., Wang, A., Chen, Q., & Li, J. (2013). Dynamic material flow analysis of zinc resources in China. Resources, Conservation and Recycling, 75,  23–31.
[10].       Liu, C., Zhu, Y., Huang, K., Yang, S., & Liang, Z. (2021). Studies of benzyl hydroxamic acid/calcium lignosulphonate addition order in the flotation separation of smithsonite from calcite. International Journal of Mining Science and Technology, 31, 1153–1158.
[11]         . Mehdilo, A., Irannajad, M., & Zarei, H. (2014). Smithsonite Flotation from Zinc Oxide Ore using Alkyl Amine Acetate Collectors. Separation Science and Technology, 49, 445–457.
[12]         . Shi, Q., Feng, Q., Zhang, G., & Deng, H. (2012). Electrokinetic properties of smithsonite and its floatability with anionic collector. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 410, 178–183.
[13]         . Xu, H., Wei, C., Li, C., Fan, G., Deng, Z., Zhou, X., & Qiu, S. (2012). Leaching of a complex sulfidic, silicate-containing zinc ore in sulfuric acid solution under oxygen pressure. Separation Science and Technology, 85, 206–212.
[14].       Xu, H., Wei, C., Li, C., Fan, G., Deng, Z., Li, M., & Li, X. (2010). Sulfuric acid leaching of zinc silicate ore under pressure. Hydrometallurgy, 105, 186–190.
[15]         . Yang, K., Zhang, L., Lv, C., Peng, J., Li, S., Ma, A., Chen, W., & Xie, F. (2017). Role of sodium citrate in leaching of low-grade and multiphase zinc oxide ore in ammonia–ammonium sulfate solution. Hydrometallurgy, 169, 534–541.
[16].       Hosseini, S.H., & Forssberg, E. (2007). Physicochemical studies of smithsonite flotation using mixed anionic/cationic collector. Minerals Engineering, 20, 621–624.
[17]         . Zhao, W., Yang, B., Yi, Y., Feng, Q., & Liu, D. (2023). Synergistic activation of smithsonite with copper-ammonium species for enhancing surface reactivity and xanthate adsorption. International Journal of Mining Science and Technology, 33, 519–527.
[18]         . Moradi, S., & Monhemius, A.J. (2011). Mixed sulphide-oxide lead and zinc ores: Problems and solutions. Minerals Engineering, 24, 1062–1076.
[19].       Zhang, S., Wen, S., Liang, G., Xian, Y., & Chen, L. (2022). Ammonia pretreatment for enhancement of Pb ions adsorption on smithsonite surface and its flotation performance. Applied Surface Science, 590, 153069.
[20].       Liao, R., Wen, S., Liu, J., Bai, S., & Feng, Q. (2024). Experimental and molecular dynamics simulation study on DDA/DDTC mixed collector co-adsorption on sulfidized smithsonite surfaces. Minerals Engineering, 205, 108493.
[21]         . Yang, J., Chen, L., Wu, D., & Zeng, J. (2023). Sodium sulfosalicylate activation mechanism on sulfidation flotation of smithsonite using dodecylamine as a collector. Minerals Engineering, 192, 107987.
[22].       Hosseini, S.H., & Forssberg, E. (2006). Adsorption studies of smithsonite flotation using dodecylamine and oleic acid. Minerals & Metallurgical Processing, 23, 87–96.
[23]         . Pereira, C.A., & Peres, A.E.C. (2005). Reagents in calamine zinc ores flotation. Minerals Engineering, 18, 275–277.
[24]         . Luo, B., Liu, Q., Deng, J., Yu, L., Lai, H., Song, C., & Li, S. (2019). Characterization of sulfide film on smithsonite surface during sulfidation processing and its response to flotation performance. Powder Technology, 351, 144–152.
[25]         . Souza, T.F., & Lima, R.M.F. (2019). Cationic flotation of smithsonite and dolomite from Brazilian ambrósia norte deposit. REM-International Engineering Journal, 72, 619–624.
[26].       Önal, G., Bulut, G., Gül, A., Kangal, O., Perek, K.T., & Arslan, F. (2005). Flotation of Aladaǧ oxide lead-zinc ores. Minerals Engineering, 18, 279–282.
[27].       Wu, D., Wen, S., Deng, J., Liu, J., & Mao, Y. (2015). Study on the sulfidation behavior of smithsonite. Applied Surface Science, 329, 315–320.
[28].       Shi, Q., Zhang, G., Feng, Q., & Deng, H. (2013). Effect of solution chemistry on the flotation system of smithsonite and calcite. International Journal of Mineral Processing, 119, 34–39.
[29]         . Ejtemaei, M., Gharabaghi, M., & Irannajad, M. (2014). A review of zinc oxide mineral beneficiation using flotation method. Advances in Colloid and Interface Science, 206,  68–78.
[30]         . Wu, D., Ma, W., Wen, S., Deng, J., & Bai, S. (2017). Enhancing the sulfidation of smithsonite by superficial dissolution with a novel complexing agent. Minerals Engineering, 114,  1–7.
[31]         . Zhang, S., Wen, S., Xian, Y., Liang, G., & Li, M. (2021). Pb ion Pre-Modification enhances the sulfidization and floatability of smithsonite. Minerals Engineering, 170, 107003.
[32]         . Zhang, S., Wen, S., Xian, Y., Zhao, L., Feng, Q., Bai, S., Han, G., & Lang, J. (2019). Lead ion modification and its enhancement for xanthate adsorption on smithsonite surface. Applied Surface Science, 498, 143801.
[33]         . Luo, Y., Ou, L., Zhang, G., Chen, J., Luo, Y., Zhou, H., Yang, H., & Yin, C. (2022). Unveiling the role of Ca ion in the sulfidation of smithsonite: A density functional theory study. Journal of Molecular Liquids, 367, 120485.
[34].       Jia, K., Feng, Q., Zhang, G., Ji, W., Zhang, W., & Yang, B. (2018). The role of S(II) and Pb(II) in xanthate flotation of smithsonite: Surface properties and mechanism. Applied Surface Science, 442, 92–100.
[35]         . Bai, S., Li, C., Fu, X., Ding, Z., & Wen, S. (2018). Promoting sulfidation of smithsonite by zinc sulfide species increase with addition of ammonium chloride and its effect on flotation performance. Minerals Engineering, 125, 190–199.
[36]         . Feng, Q., Wang, M., Zhang, G., Zhao, W., & Han, G. (2023). Enhanced adsorption of sulfide and xanthate on smithsonite surfaces by lead activation and implications for flotation intensification. Separation & Purification Technology, 307, 122772.
[37]         . Xiao, Y., Peng, S., Tong, X., Xie, R., & Ma, Y. (2025). Enhancing the separation of galena from sphalerite by the synergistic effect of calcium oxide and sodium thioglycolate. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 720, 137189.
[38]         . Smart, R.S.C., Skinner, W.M., & Gerson, A.R. (1999). XPS of Sulphide Mineral Surfaces : Metal-deficient, Polysulphides, Defects and Elemental Sulphur. Surface and Interface Analysis, 105, 101–105.
[39]         . Herron, S.M., Lawal, Q.O., & Bent, S.F. (2015). Polysulfide ligand exchange on zinc sulfide nanocrystal surfaces for improved film formation. Applied Surface Science, 359, 106–113.
[40].       Lau, W.M., Kwok, R.W.M., & Ingrey, S. (1992). Controlling surface band-bending of InP with polysulfide treatments. Surface Science, 271, 579–586.
[41]         . Song, H.S., Park, M.G., Ahn, W., Lim, S.N., Yi, K.B., Croiset, E., Chen, Z., & Nam, S.C. (2014). Enhanced adsorption of hydrogen sulfide and regeneration ability on the composites of zinc oxide with reduced graphite oxide. Chemical Engineering Journal, 253, 264–273.
[42]         . Chai, R., Liu, Y., Liu, Q., & Xin, J. (2021). Interaction mechanism of calcite and four representative organic molecules: Experiments and DFT study. Colloids and Surfaces A: Physicochemical and Engineering Aspects,  612,  125822.
[43].       Jin, D., Sun, R., Wang, G., Deng, J., & Zhang, X. (2023). Flotation separation of fluorite and calcite using anhydrous glucose and aluminum sulfate as a combined depressant. Applied Surface Science, 624, 157089.
[44]         . Zhang, S., Xian, Y., Wen, S., & Liang, G. (2022). Enhancement of xanthate adsorption on lead-modified and sulfurized smithsonite surface in the presence of ammonia. Minerals Engineering, 189, 107872.
[45]         . Zhang, Y., Zhao, W., Han, G., & Feng, Q. (2025). A novel activation method for regulating surface characteristics and flotation performance of smithsonite: XPS, SEM-EDS, AFM, ToF-SIMS and FT-IR studies. Separation Purification Technology, 352, 128276.
[46]         . Zhao, W., Liu, D., Wen, S., & Feng, Q. (2019). Surface modification of hemimorphite with lead ions and its effect on flotation and oleate adsorption. Applied Surface Science, 483, 849–858.
[47]         . Jia, K., Feng, Q., Zhang, G., Shi, Q., & Chang, Z. (2017). Understanding the roles of Na2S and Pb(II)in the flotation of hemimorphite. Minerals Engineering, 111, 167–173.
[48]         . Li, R., Shao, Y., Li, J., Liu, C., Chen, H., Meng, X., & Jia, X. (2025). Utilization of fluorine ions to improve the sulfidization process and flotation recovery of smithsonite. Separation & Purification Technology, 376, 134029.
[49]         . Zhu, G., Zhao, Y., Zheng, X., Wang, Y., Zheng, H., & Lu, D. (2020). Surface features and flotation behaviors of spodumene as influenced by acid and alkali treatments. Applied Surface Science, 507, 145058.
[50]         . Zuo, Q., Wu, D., Cao, J., Wang, Z., Shuming, W., Huang, L., & Chen, H. (2023). Surface modification of hemimorphite via double-complexation by ammonium fluoride and copper ion to promote sulfidation. Applied Surface Science, 612, 155797.
[51]         . Guan, Z., Liao, R., Zhang, Y., Feng, Q., & Wen, S. (2024). Experimental and simulation study on the flotation separation of smithsonite from dolomite using phosphoryl carboxyl copolymer as a novel depressant. Separation & Purification Technology, 346, 127488.
[52]         . Yang, W., Tang, Y., Huang, B., Han, G., & Feng, Q. (2025). Experimental and molecular dynamics simulation insights into enhanced flotation of sulfidized smithsonite in a Cu–Pb dual activation system. Green and Smart Mining Engineering, 2, 8–17.
[53]         . Zhao, W., Wang, M., Yang, B., Feng, Q., & Liu, D. (2022). Enhanced sulfidization flotation mechanism of smithsonite in the synergistic activation system of copper–ammonium species. Minerals Engineering, 187, 107796.
[54]         . Bai, X., Liu, J., Wen, S., Wang, Y., & Lin, Y. (2020). Effect of ammonium salt on the stability of surface sulfide layer of smithsonite and its flotation performance. Applied Surface Science, 514, 145851.
[55]         . Cai, J., Ma, Y., Su, C., Lai, H., Shen, P., Liu, D., & Pei, B. (2023). New insight into enhancing sulfurization of azurite with ethylenediamine and its response to xanthate adsorption. Journal of Molecular Liquids, 389, 122865.
[56]         . Grich, A., Bouzid, T., Naboulsi, A., Regti, A., El Himri, M., & El Haddad, M. (2024). Synthesis and optimization of activated carbon from Doum (Chamaerops humilis) fiber via pyrolysis-assisted H3PO4 activation for removal of bisphenol A and α-Naphthol. Diamond and Related Materials, 145, 111061.
[57]         . Mohammadi, I., Shahrabi, T., Mahdavian, M., & Izadi, M. (2020). Cerium/diethyldithiocarbamate complex as a novel corrosion inhibitive pigment for AA2024-T3. Scientific Reports, 10, 1–15.
[58].       Mohammadi, I., Shahrabi, T., Mahdavian, M., & Izadi, M. (2021). Chemical modification of LDH conversion coating with diethyldithiocarbamate as a novel anti-corrosive film for AA2024-T3. Journal of Industrial and Engineering Chemistry, 95, 134–147.
[59]         . Touati, S., & Meniai, A.H. (2012). Solvent extraction of Cu (II) from sulphuric acid by means of sodium diethyldithiocarbamate and characterization of the formed complex. Theoretical Foundations of Chemical Engineering, 46, 719–726.
[60]         . Cordeiro, A.P., Feuser, P.E., Figueiredo, P.G., Da Cunha, E.S., Martinez, G.R., Machado-de-Ávila, R.A., Rocha, M.E.M., de Araújo, P.H.H., & Sayer, C. (2021). In vitro synergic activity of diethyldithiocarbamate and 4-nitrochalcone loaded in beeswax nanoparticles against melanoma (B16F10) cells. Materials Science and Engineering: C, 120, 111651.
[61]         . Mazur, K.L., Feuser, P.E., Valério, A., Poester Cordeiro, A., De Oliveira, Assolini, C.I., J.P., Pavanelli, W.R., Sayer, C., & Araújo, P.H.H. (2019). Diethyldithiocarbamate loaded in beeswax-copaiba oil nanoparticles obtained by solventless double emulsion technique promote promastigote death in vitro. Colloids and Surfaces B: Biointerfaces, 176, 507–512.
[62]         . Henry, D.G., Watson, J.S., & John, C.M. (2017). Assessing and calibrating the ATR-FTIR approach as a carbonate rock characterization tool. Sedimentary Geology, 347, 36–52.
[63]         . Sun, H., Niu, F., & Zhang, J. (2021). Investigation on the flotation separation of smithsonite from calcite using calcium lignosulphonate as depressant. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 630, 127571.
[64].       Liu, W., Peng, X., Liu, W., Wang, X., Zhao, Q., & Wang, B. (2020). Effect mechanism of the iso-propanol substituent on amine collectors in the flotation of quartz and magnesite. Powder Technology, 360, 1117–1125.
[65]         . Ibrahim, A.M., Wang, Elnabi, H., G., Yousif, J.A., & Liu, D. (2025). Effect of sodium diethyldithiocarbamate ( DDTC ) and xanthate collaborative collection in malachite sulfurization flotation: Enhancement and mechanisms. Physicochemical Problems of Mineral Processing, 61, 203078.