Chemical speciation in mining affected waters: the case study of Asarel-Medet mine

The inorganic chemical species in Maresh and Luda Yana rivers affected by the Cu– Mo Asarel-Medet mine, Bulgaria were determined during a low-flow and a high-flow period. The mining activities, the weathering and the oxidation processes strongly influenced the physicochemical processes in the whole water system. The main pollution source was a small lake receiving the acid effluents of the mining activities. High levels of SO₄ ^2???, Cu, Mg, Al, Mn and Fe were determined at the mining polluted and affected stations. Cu^2?+? and CuCO₃ ⁰ species (1:1) were present in the reference waters and Cu^2?+? and CuSO₄ ⁰ species (1:1) in the polluted and affected waters; Cu^2?+? species was dominating downstream. Me^2?+? followed by $\rm{MeSO}_{4}^{\kern3pt{0}}$ (Me = Mn, Zn, Cd and Pb), $\rm{PbCO}_{3}^{\kern3pt{0}}$ and $\rm{PbHCO}_{3}^{\kern3pt{+}}$ species as well as $\rm{Fe(OH)}_{2}^{\kern3pt{+}}$ , $\rm{Al(OH)}_{4}^{\kern3pt{-}}$ , $\rm{Al(OH)}_{2}^{\kern3pt{+}}$ , $\rm{Al(OH)}_{3}^{\kern3pt{0}}$ were prevailing in the system. $\rm{MeSO}_{4}^{\kern3pt{+}}$ and $\rm{Me(SO}_{4})_{2}^{\kern3pt{-}}$ (Me = Fe, Al), $\rm{Me(SO}_{4})_{2}^{\kern3pt{2-}}$ (Me = Zn, Cd and Pb), $\rm{Me(SO}_{4})_{3}^{\kern3pt{4-}}$ (Me = Zn, Cd) and $\rm{Cd(SO}_{4})_{4}^{\kern3pt{6-}}$ species polluted and affected waters. The major elements K and Na were mainly Me^?+? species, whereas Ca and Mg were Me^2?+? and $\rm{MeSO}_{4}^{\kern3pt{0}}$ species in different ratios. The concentration of concentration of $\rm{NO}_{2}^{\kern3pt{-}}$ , $\rm{NO}_{3}^{\kern3pt{-}}$ and $\rm{NH}_{4}^{\kern3pt{+}}$ species as well as complex phosphorous species such as H₂ $\rm{PO}_{4}^{\kern3pt{-}}$ , $\rm{FeHPO}_{4}^{\kern3pt{+}}$ , $\rm{HPO}_{4}^{\kern4pt{2-}}$ , $\rm{CaPO}_{4}^{\kern3pt{-}}$ , $\rm{CaHPO}_{4}^{\kern3pt{0}}$ and $\rm{MgHPO}_{4}^{\kern3pt{0}}$ were also calculated. The trace element concentrations decreased downstream due to dilution, sorption processes and precipitation, but the percentage of free metal species, which are more toxic, increased. An exception was iron and aluminum of which the dominant hydroxy colloidal and sulphate species were easily incorporated into the suspended phase.