Characterization and Geochemical Modeling of Cu and Zn Sorption Using Mineral Systems Injected with Iron Sulfide: Case Study of Mine Waste Water, Wales, United Kingdom
World Journal of Applied Chemistry
Volume 2, Issue 1, February 2017, Pages: 13-23
Received: Nov. 27, 2016; Accepted: Dec. 24, 2016; Published: Feb. 3, 2017
Views 2864      Downloads 112
Davidson Egirani, Faculty of Science, Niger Delta University, Wilberforce Island, Nigeria
Napoleon Wessey, Faculty of Science, Niger Delta University, Wilberforce Island, Nigeria
Shukla Acharjee, Centre for Studies in Geography, Dibrugarh University, Assam, India
Article Tools
Follow on us
Sorption of Cu and Zn was investigated using single and mixed mineral systems under sulfidic-anoxic condition to treat wastewater obtained from disused mine pits at Parys Mountain in, United Kingdom. Water courses are the recipients of these contaminants. In these water courses fishing activities exist. Attempt was made to reduce the Cu and Zn levels intake in the watercourses using mineral systems of clays and goethite. These were tested with the mine waste water for characterization of copper and zinc removal at variable pH, solid concentration and contact time. In addition, levels of saturation of hydroxyl complexes were modeled. Batch reactions conducted at ambient temperature (23±2°C) reveal all systems of assorted minerals sorbed more Cu than Zn. In addition, Cu sorbed on iron sulfide exhibited increase in sorption with increasing pH. There was cross cutting effect of Cu and Zn sorbed on iron sulfide at pH 6 and Cu sorbed on goethite at about pH 7, These indicate similar metal removal characteristics. Differences in removal of copper and zinc ions may be assigned to outer sphere complexation and specific adsorption of copper and zinc ions. Non-promotive Cp effect (i.e. decrease in metal removal with increase in concentration of particle) was observed in all minerals. This effect may be assigned to increase in aggregation of the mineral particle size. Ageing characterization progresses as residence time was increased. This may be assigned thiol (=S-H) and hydroxyl (=Me-OH) groups and sites of reactions. There is no link to stable hydroxylation of copper and zinc species that could significantly contribute to the removal of these metals.
Ageing, Cu-Zn, Mixed Mineral Systems, PH Solution Composition
To cite this article
Davidson Egirani, Napoleon Wessey, Shukla Acharjee, Characterization and Geochemical Modeling of Cu and Zn Sorption Using Mineral Systems Injected with Iron Sulfide: Case Study of Mine Waste Water, Wales, United Kingdom, World Journal of Applied Chemistry. Vol. 2, No. 1, 2017, pp. 13-23. doi: 10.11648/j.wjac.20170201.13
Copyright © 2017 Authors retain the copyright of this article.
This article is an open access article distributed under the Creative Commons Attribution License ( which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Egirani, D. E. Andrews, J. E Baker, A. R. (2013). “Characterization of Sorption and Quantitative Analysis of Hydroxyl Complexes of Cu and Zn In Aqueous Solution: The Interactive Effects of Mine Wastewater mixed Mineral Systems,” Inter. J. Recent Scientific Research, 4, 469-475.
Ayari, F. Srasra, E. Trabelsi-Ayadi, M. (2007). “Retention of lead from an aqueous solution by use of bentonite as adsorbent for reducing leaching from industrial effluents,” Desalination, 206, 270–278.
Brower, J. B. Ryan, R. L Pazirande, M. (1997). “Comparison of ion exchange resins and biosorbings for the removal of heavy metals from plating factory wastewater,” Environmental Science & Technology, 31, 2910-2914.
Veli, S. Alyüz, B. (2007). “Adsorption of copper and zinc from aqueous solutions by using natural clay,” J. Hazard. Mater,. 149,226–233.
Megateli, S. Semsari, S. Couderchet, M. (2009). “Toxicity and removal of heavy metals (cadmium, copper, and zinc) by Lemna gibba,” Ecotoxicol. Environ. Saf., 72, 1774–1780.
Chan, S. S. Chow, H. Wong, M. H. (1991). “Microalge as a bioabsorbents for treating mixture of electroplating and sewage effluent,” Biomed. Environ. Sci. 4, 250–260.
Zhang, Y. Yang, Y. L. L. Ma, X. Wang, L. Ye, Z. (2010). “Characterization and adsorption mechanism of Zn2+ removal by PVA/EDTA resin in polluted water,” J. Hazard. Mater, 178,1046–1054.
Fernández-Calviño, D. Pérez-Novo, C. Bermúdez-Couso, A. López-Periago, E. Arias-Estévez, M. (2010). “Batch and stirred flow reactor experiments on Zn sorption in acid soils Cu competition,” Geoderma, 159, 417–424.
Terminghoff, E.J. M. Van Der Zee, S. A. Keizer, M. G. (1994). “The desorption and speciation of copper in a sandy soil,” J. Soil Sci,. 158, 398–407.
Altin, O. Özbelge, H. Ö. Dogu, T. (1999). “Effect of pH in an aqueous medium on the surface area, pore size distribution, density, and porosity of montmorillonite,” J. Colloid Interface Sci,. 217, 19–27.
Kitano, Y. Okumura, M. Idogaki, M. (1980). “Abnormal behaviour of Cu2+ and Zn ions in parent solution at the early stage of calcite formations,” Geochem. J., 14, 167–175.
Banks, D. Burke, S. P. Gray, C. G. (1997). “Drainage and other ferruginous waters in north Derbyshire and south Yorkshire, U. K,” J. Eng. Geol,. 30, 257–280.
Schlegel, M. L Manceau, A., Charlet, L Chateigner, D. Hazemann, J.-L (2001). “Sorption of metal ions on clay minerals. III. Nucleation and epitaxial growth of Zn on the edges of hectorite,” Geochimica et Cosmochimica Acta, 65, 4155-4170.
Younger, P L, Banwert, S A, Hedin, R S. (2002). “Mine water, hydrology, pollution and remediation,” Springer [Ed.], London, 16, 442 p.
Appel, C. Ma, L. (2002). “Concentration, pH, and surface charge effects on. Cd and Pb sorption in tropical soils,” J. Environ. Qual., 31, 581-589.
Song, H. Yim, G-J. Ji, S-W. Neculita, C. M. Hwang, T. (2012). “Pilot-scale passive bioreactors for the treatment of acid mine drainage: Efficiency of mushroom compost vs. mixed substrates for metal removal,” J. Environ. Mgt., 111, 150-158.
Holan, Z. R. Volesky, B. (1994). “Biosorption of lead and nickel by biomass of marine algae,” Biotechnol. Bioengery, 43, 1001–1009.
Akar, T. Kaynak, Z. Ulusoy,. S. Yuvaci, D. Ozsari, G. Akar, S. T. (2009). “Enhanced biosorption of nickel(II) ions by silica-gel-immobilized waste biomass: biosorption characteristics in batch and dynamic flow mode,” J. Hazard. Mater, 163, 1134–1141.
Shao, W. Chen, L Lu, L. Luo, F. (2011). “Removal of lead (II) from aqueous solution by a new biosorption material by immobilizing Cyanex272 in cornstalks,” Desalination, 265, 177–183.
Dzombak, D. A. Morel, F. (1999). “Surface complexation modeling: hydrous ferric oxide,” Wiley, New York, pp. 20.
Lutzenkirchen, J. (2001). “Ionic strength effects on cation sorption to oxides: macroscopic observations and their significance in microscopic interpretation,” J. Colloid Interface Sci. 65, 149–155.
Devotta, I. Mashelkar, R. A. (1996). “Competitive diffusion–adsorption of polymers of differing chain lengths on solid surfaces,” Chem. Eng. Sci. 51, 561–569.
Kamei,. G. Ohmoto, H. (2000). “The kinetics of reactions between pyrite and O2-bearing water revealed from in situ monitoring DO, Eh and pH in a closed system,” Geochim. Cosmochim. Acta 64, 2585–2601.
Ridge, A. C, Sedlak, D. L. (2004). “Copper and zinc complexes with EDTA during municipal wastewater treatment,” J. Water Res. 38, 921–932.
Fotovat, A. Naidu R. Sumner, M. E. (1994). “Ionic-strength and ph effects on the sorption of cadmium and the surface-charge of soils,” European J. Soil Science, 45 (4), 419-429.
Philips, I. R. (1999). “Copper, lead, cadmium and zinc sorption by waterlogged and air-dry soil,” J. Soil Contam,. 8, 343–364.
Medina, M. Tapia, J. Pacheco, S. Espinosa, M. Rodriguez, R. (2010). “Adsorption of lead ions in aqueous solution using silica–alumina nanoparticles,” J. Non-Cryst. Solids, 356, 383–387.
Tripathy, S. S. Kanungo, S. B. (2005). “Adsorption of Co2+, Ni2+, Cu2+ and Zn2+ from 0.5 M NaCl and major ion sea water,” J. Colloids Interface Sci., 28, 30–38.
Naeem, A. Siddique, M. T. Mustafa, S. Kim, Y. Dilara, B. (2009). “Cation exchange removal of Pb from aqueous solution by sorption onto NiO,” J. Hazard. Mater., 168, 364–368.
Morrison, S. J. Metzler, D. R. Dwyer, B. P. (2002). “Removal of As, Mn, Mo, Se, U, V and Zn from groundwater by zero-valent iron in a passive treatment cell: reaction progress modeling,” J. Contam. Hydrol., 56, 99–116.
Benjamin, M. M., (1983). “Adsorption and surface precipitation of metals of amorphous iron oxyhidroxide,” Environ., Sci., Technol., 17, 686–692.
Safdar, M. Mustafa, S. Naeem, A. Mahmood, T. Waseem, M. Tasleem, S. Ahmad, T. Siddique, M. T. (2011). “Effect of sorption on Co (II), Cu (II), Ni (II) and Zn(II) ions precipitation,” Desalination, 266, 171–174.
Parkman, R. H. Charnock, J. M. Bryan, N. D. Livens, F. R. Vaughan, D. J. (1999). “Reactions of copper and cadmium ions in aqueous solution with goethite, lepidocrocite, mackinawite, and pyrite,” American Mineralogist, 84, 407–419.
Gammonsa C. H. Frandsen, A. K. (2001). “Fate and transport of metals in H2S-rich waters at a treatment Wetland,” Geochem. Trans. 2, 1-15.
Kumar, R. Barakat, M. A. Daza, Y. A. Woodcock, H. L. Kuhn, J. N. (2013). “EDTA functionalized silica for removal of Cu(II), Zn(II) and Ni(II) from aqueous solution,” J. Colloid and Interface Sci., 408,200-205.
Gomes, E. C. C. de Sousa, A. F. Vasconcelos, P. H. M. Melo, D. Q. Diogenes, I. C. N. de Sousa, E. H. S. (2013). “Synthesis of bifunctional mesoporous silica spheres as potential adsorbent for ions in solution,” Chem. Eng. J., 214, 27-33.
Wu, S. Kuschk, P. Wiessner, A. Müller, J. Saad, R. A. B. Dong, R. (2013). “Sulphur transformations in constructed wetlands for wastewater treatment: A review,” Ecological Engineering, 52, 278–289.
Brix, H. (1999). “How ‘green’ are aquaculture, constructed wetlands and conventional wastewater treatment systems,” Water Sci. Technol. 40 (3), 45–50.
Gopal, B. (1999). “Natural and constructed wetlands for wastewater treatment: potentials and problems,” Water Sci. Technol., 40 (3), 27–35.
Vymazal, J. (2005).” Horizontal sub-surface flow and hybrid constructed wetlands systems for wastewater treatment,” Ecol. Eng,. 25, 478–490.
Gubbuk, I. H. (2011). “Isotherms and thermodynamics for the sorption of heavy metal ions onto functionalized sporopollenin,” J. Hazard. Mater., 186, 416–422.
Blesa, M. A. Magaz, G. Salfity, J.. A. Weisz, A. D. (1997). “Structure and reactivity of colloidal metal particles immersed in water,” Solid State Ionics, 101–103, 1235–1241.
Tombacz, E. Filipcseis, G. Szekeres, M. Gingl, Z. (1999). “Particle aggregation in complex aquatic systems,” J. Colloids Surf., 15, 233–244.
Bonnissel-Gissinger, P. Alnot, M. Ehrhardt, J. J. Behra, P. (1998). “surface oxidation of iron sulfide as a function of pH,” Environ. Sci. Technol., 32, 2839-2845, 1998.
Morse, J. W. Arakaki, T. (1993). “Adsorption and coprecipitation of divalent metals with mackinawite (FeS),” Geochim Cosmochim Acta, 57, 3635–3640.
Morse, J. W. Luther, G. W. (1999). "Chemical influences on trace metal-sulfide interactions in anoxic sediments,” Geochemical Et Cosmochimica Acta, 63 (19-20), 3373-3378.
Odom, J. M. Singleton, J. R. (1983). “The sulfate-reducing bacteria: Contemporary perspectives,” Springer- Verlag, New York, ISBN 0-387-97865-8.
Zagury, G. J. Kulnieks, V. I. Neculita, C. M. (2006). “Characterization and reactivity assessment of organic substrates for sulphate-reducing bacteria in acid mine drainage treatment,” Chemosphere, 64, 944-954.
Neal, A. L. Techkarnjanaruk, S. Dohnalkova, A. McCready D. Peyton, B. M. Geesey G. G. (2001).,” Iron sulfides and sulfur species produced at hematite surfaces in the presence of sulfate-reducing bacteria,” Geochimica et Cosmochimica Acta, 65, 223-235.
Barrett, T. J. MacLean, W. H, Tennant, S. C. (2001). “Volcanic sequence and alteration at the Parys Mountain Volcanic-Hosted Massive Sulfide Deposit, Wales, United Kingdom: Applications of Immobile Element Lithogeochemistry,” Economic Geology, 96: 1279-1305.
Cooper, D. C, Nutt, M. J, C, Morgan, D. J. (1982). “Reconnaissance geochemical survey of Anglesey,” Institute of Geology Science Report, 90, 4.
Swallow, M. (1990). “Parys Mountain a mine in prospect, Mining Magazine,” 163, 334–336.
Nelson, Y. M. (2002). “Effect of oxide formation mechanisms on lead adsorption by biogenic manganese (hydr) oxides, iron (hydr) oxides, and their mixtures,” Environ. Sci. and Technol., 36, 421-425.
Point on, C. R, Ixer, R. A. (1980). “Acid mine drainage in Wales and influence of ochre precipitation on water chemistry,” Transactions of the Institute of Mining and Metallurgy, 89, 143-155.
Engler, R, Patrick, W, (1973). “Sulfate reduction and sulfide oxidation in flooded soil as affected by chemical oxidants,” Soil Science, 119, 217-221.
Walter, K. Johnson, D, (1992). “Microbiological and chemical characteristics of an acidic stream draining a disused copper mine,” Environ. Pollution, 76: 169-175.
Egirani, D. E Baker, A. R. Andrews,, J. E, (2005b). “Copper and Zinc removal from aqueous solution by mixed mineral systems I: Reactivity and removal kinetics,”, J. Colloid and Interface Sci., 291, 319–32.
Parkhurst, D. L Appelo, C. A. J, (1999). “User's Guide to PHREEQC (Version 2), A computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations,” U. S. Geological Survey Water-Resources Investigations Paper, 99-4259, 312.
Dunnette, D. A. Chynoweth, D. P. Mancy, K. H. (1985). “The source of hydrogen sulfide in anoxic Sediment,” Water Res., I9 (7), 875-884.
Wilkin, R. T. Barnes, H. L. (1996). “Pyrite formation by reactions of iron mono-sulfides with dissolved inorganic and organic sulfur species,” Geochim Cosmochim Acta, 60, 4167.
Brunauer, S. Emmett, P. H. Teller, E. (1938). “Adsorption of gases in multimolecular layers”, J. Am. Chem. Soc. 60, 309–319.
Science Publishing Group
1 Rockefeller Plaza,
10th and 11th Floors,
New York, NY 10020
Tel: (001)347-983-5186