Enhanced removal of high-As(Ⅲ)from Cl(-Ⅰ)-diluted SO_(4)(-Ⅱ)-rich wastewater at pH 2.3 via mixed tooeleite and(Cl(-Ⅰ)-free)ferric arsenite hydroxychloride formation

An advanced cost-saving method of removal of high-As(Ⅲ)from SO_(4)(-Ⅱ)-rich metallurgical wastewater has been developed by diluting the SO_(4)(-Ⅱ)content with As(Ⅲ)-Cl(-Ⅰ)-rich metallurgical wastewater and then by the direct precipitation of As(Ⅲ)with Fe(Ⅲ)at pH 2.3.As(Ⅲ)removal at various SO_(4)(-Ⅱ)/Cl(-Ⅰ)molar ratios and temperatures was investigated.The results showed that 65.2–98.2%of As(Ⅲ)immobilization into solids occurred at the SO_(4)(-Ⅱ)/Cl(-I)molar ratios of 1:1–32 and 15–60℃in 3 days,which were far higher than those in aqueous sole SO4(-Ⅱ)or Cl(-Ⅰ)media at the equimolar SO_(4)(-Ⅱ)or Cl(-Ⅰ)and the same temperature.SO_(4)(-Ⅱ)/Cl(-Ⅰ)molar ratio of 1:4 and 25℃were optimal conditions to reach the As removal maximum.Mixed aqueous SO4(-Ⅱ)and Cl(-Ⅰ)played a synergetic role in the main tooeleite formation together with(Cl(-Ⅰ)-free)ferric arsenite hydroxychloride(FAHC)involving the substitution of AsO_(3)^(3−)for Cl(-Ⅰ)for enhanced As fixation.The competitive complexation among FeH_(2)AsO_(3)^(2+),FeSO_(4)^(+)and FeCl^(2+)complexes was the main mechanism for the maximum As(Ⅲ)precipitation at the SO4(-Ⅱ)/Cl(-I)molar ratio of 1:4.Low As(Ⅲ)immobilization at high temperature with increased Fe(Ⅲ)hydrolysis was due to the formation of As(Ⅲ)-bearing ferrihydrite with the relatively high Fe/As molar ratio at acidic pH.