Influence of natural organic matter and ionic composition on the kinetics and structure of hematite colloid aggregation: Implications to iron depletion in estuaries

The stability and aggregation behavior of iron oxide colloids in natural waters play an important role in controlling the fate, transport, and bioavailability of trace metals. Time-resolved dynamic light scattering experiments were carried out in a study of the aggregation kinetics and aggregate structure of natural organic matter (NOM) coated hematite colloids and bare hematite colloids. The aggregation behavior was examined over a range of solution chemistries, by adjusting the concentration of the supporting electrolyte-NaCl, CaCl2, or simulated seawater. With the solution pH adjusted so that NOM-coated and bare hematite colloids were at the same zeta potential, we observed a significant difference in colloid stability which results from the stability imparted to the colloids by the adsorbed NOM macromolecules. This enhanced stability of NOM-coated hematite colloids was not observed with CaCl2. Aggregate form expressed as fractal dimension was determined for both NOM-coated and bare hematite aggregates in both NaCl and CaCl2. The fractal dimensions of aggregates formed in the diffusion-limited regime indicate slightly more loosely packed aggregates for bare hematite than theory predicts. For NOM-coated hematite, a small decrease in fractal dimension was observed when the solution composition changed from NaCl to CaCl2. For systems in the reaction-limited regime, the measured fractal dimensions agreed with those in the literature. Colloid aggregation was also studied in synthetic seawater, a mixed cation system to simulate estuarine mixing. Those results describe the important phenomena of iron oxide aggregation and sedimentation in estuaries. When compared to field data from the Mullica Estuary, U.S.A., it is shown that collision efficiency is a good predictor of the iron removal in this natural system.