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.

Characterization of Fe5(AsO3)3Cl2(OH)4·5H2O,a new ferric arsenite hydroxychloride precipitated from FeCl3-As2O3-HCl solutions relevant to arsenic immobilization

Tooeleite(Fe6(As03)4 SO4(OH)4·4 H2 O)is widely precipitated for direct As(III)removal from sulfate-rich industrial effluents.However,whether or not Fe(III)-As(III)-Cl(-I)precipitate is produced in chloridizing leaching media for As immobilization is almost unknown.This work founded the existence of ferric arsenite(hydroxy)chloride as a new mineral for As(III)removal.Its chemical composition and solid characterization were subsequently studied by using scanning electron microscope with an energy dispersive spectrometer(SEM-EDS),X-ray diffraction(XRD),infrared(FT-IR),Raman spectroscopy and thermogravimetric(TG)curve.The results showed the formation of a yellow precipitate after 3-days reaction of Fe(III)/As(III)with molar ratio≈1.7 in chloride solution at pH 2.3 neutralized with NaOH.Compared with tooeleite,chemical analysis and solid characterization indicated that Cl(-I)replaces S04(-II)producing ferric arsenite hydroxychloride with formula Fe5(As03)3-Cl2(OH)4·5 H2 O.This new plate shaped solid showed better crytallinity than tooeleite,although it has similar morphology and characteristic bands to tooeleite.The FT-IR bands at 628,964 cm-1 and the Raman bands at 448,610,961 cm-1 were assigned to Fe-O or As(Ⅲ)-O-Fe or As(Ⅲ)-O bending/stretching vibration,indicating that both arsenite and chloride substituted for the position of sulfate for ferric arsenite hydro xychloride produced due to the lack of the SO42-vibrations.Cl-(I)also contributed to increase As removal efficiency in aqueous sulfate media under acidic pH conditions via the probable formation of sulfatechloride ferric arsenite.