Coagulation kinetics of humic aggregates in mono- and di-valent electrolyte solutions.

Coagulation behaviors of humic acids (HAs) aggregates in electrolyte solutions at different pHs, valences and concentrations of electrolyte cations were investigated using dynamic light scattering technique in combination of other analytical tools. For monovalent electrolyte sodium chloride (NaCl) solution, at its low concentrations the average hydrodynamic radius (<Rh>) of aggregates kept nearly constant. However, at high NaCl concentrations, <Rh> could be scaled to the time t as <Rh> ∝ t(a), suggesting a diffusion-limited colloid aggregation (DLCA). The coagulation value of NaCl in a buffer at pH 7.1 was calculated to be in a range of 61.3-84.4 mM. Divalent cation Mg(2+) was far more effective in enhancing the HA coagulation, as evidenced by a lower coagulation value (between 1.0 and 1.7 mM) and a more rapid coagulation rate. Such an enhancement could be explained by the combined effects of electrostatic repulsion, complexation and bridging. The highest coagulation rate (d<Rh>/dt) and coagulation value at different pHs followed the order of: acidic > neutral > alkaline, and alkaline > neutral > acidic, respectively. Such a difference was associated with the extent of hydrogen bond and electrostatic repulsion at different protonation/deprotonation states of carboxyl and phenolic -OH groups. Transmission electron microscopic imaging reveals that HA was predominantly globular aggregates with a rough periphery at pH 5.26, and was changed to smooth spherical particles at pH 10.00. These results are useful for better understanding the coagulation behaviors of HAs in both natural and engineered aqueous systems.