Chemical speciation of Co, Ni, Cu, and Zn in mine effluents and effects of dilution of the effluent on release of the above metals from their metal–dissolved organic carbon (DOC) complexes

• Published in: Analytica chimica acta 2006-07, Vol.571 (2), p.260-269
• Main Authors: Chakraborty, Parthasarathi, Chakrabarti, Chuni L.
• Format: Article
• Language: English
• Subjects: Adsorptive cathodic stripping voltammetry; Analytical chemistry; Chemistry; Competing ligand exchange method; Electrochemical methods; Exact sciences and technology; Freshwater; Ligand field stabilization energy; Metal–DOC bond; Mine effluents
• ISSN: 0003-2670; 1873-4324
• DOI: 10.1016/j.aca.2006.04.069

The paper explores the lability of DOC complexes of Co, Ni, Cu, and Zn in the mining effluent, and investigates the effects of dilution of the effluent on the release of metals from the metal–DOC complexes. This study was done using competing ligand exchange method in conjunction with adsorptive cathodic stripping voltammetry on effluent samples from Copper Cliff Mine, Sudbury, Canada, using two samples of the effluent: one, undiluted (100%) effluent, and the other, diluted (45%) effluent. The dilution was done with tap water in order to determine the effects of dilution on the metal complexes in the effluents when they were discharged into receiving streams of freshwaters. The dilution of the effluent had a small effect on release of Cu from the Cu–DOC complexes, but had a much greater effect on the release of Zn from the Zn–DOC complexes. The release of Ni and Co from their DOC complexes decreased drastically on dilution of the effluent. The much greater release of Cu from the Cu–DOC complexes compared to the release of Ni, Co, and Zn from their DOC complexes in both the undiluted and the diluted effluent was probably due to the higher absolute concentration of Cu and the higher [Cu]/[DOC] ratio. The drastic decrease in the release of Ni and Co from the Ni– and Co–DOC complexes in the diluted (45%) effluent compared with the undiluted (100%) effluent probably resulted from strengthening of the metal–DOC bond due to the reduced screening of charges by a smaller concentration of Ca 2+ in the diluted (45%) effluent. This work also shows that change in the ionic strength produces conformational changes in and in aggregation and precipitation of the DOC and also changes in electrostatic interactions between the metal cations and the humate polyanions.