A study of coagulation mechanisms of polyferric sulfate reacting with humic acid using a fluorescence-quenching method

A fluorescence-quenching method is developed to assess the effect of pH on the coagulation mechanism of humic acids (HA) reacting with metal ions. A polyferric sulfate (PFS) synthesized in our laboratory is adopted as the coagulant to simplify the hydrolysis process and increase the experimental precision. The following results are discovered. When the concentration of PFS increases from 2 to 10 mg/L, the effective pH range of HA removal changes from 4.0–5.0 to 4.0–7.5. At increased coagulation pH, the ferric ions may still react with HA but unable to neutralize the surface charge completely. The residual concentrations of HA measured by fluorescence spectrophotometer are lower than those by TOC, as a consequence of the fluorescence-quenching effect. This demonstrates that the coagulation of HA by PFS at low pH is mainly due to charge-neutralization. The adsorption of the HA on the pre-formed iron hydroxide flocs is accompanied by the dissociation of Fe ions from the floc structure until the equilibrium has been reached, which is evidenced by the presence of the Fe-HA complexes in the solution during adsorption experiment. This is quite different from the characteristics of flocs formed by PFS associated with HA in the coagulation. Within the pH range investigated, the complex-formation and the hydrolysis are the two competitive reactions happened between the hydroxide ions in solution and the functional groups of HA. Therefore, the removal of HA is not caused by adsorbing onto the iron hydroxide resulted from PFS hydrolysis, but through the complex-formation between the PFS and the HA.