Abiotic reversible self-assembly of fulvic and humic acid aggregates in low electrolytic conductivity solutions by dynamic light scattering and zeta potential investigation.

The aggregation of humic substances and their interaction with filtration media (membranes, soils) has implications for our understanding of membrane fouling during water treatment, the facilitated transport of contaminants, and the transport of organic matter through the microbial loop. To investigate the aggregation of fulvic and humic acids in low electrolytic conductivity solutions, laboratory studies of simulated environmental water samples as well as actual environmental water samples were examined. Intensity-, volume-, and number-based particle size distributions (PSDs) were obtained by dynamic light scattering. Aggregates were categorized into three ranges, i.e., 10-100 nm, 100-1000 nm, and >1 μm. Individual biomacromolecules and the aggregates between 10 nm and 1 μm were presumed to be precursors for the formation of a large 5-μm-sized-particle. The self-assembly of the large-in-volume, few-in-number, 5-μm-sized particle was observed in real-time and occurred in unfiltered samples and in samples filtered (0.45 μm) at a nominal size one order of magnitude smaller. The supramicrometer-sized particle formed, dissipated, and spontaneously re-formed over turbulent/quiescent cycles in the presence of sodium azide indicating reversible abiotic self-assembly. Zeta potential analyses demonstrated that colloidal stability increased as concentration increased. DLS studies of the environmental water samples were comparable to those of the simulated laboratory samples. The operational range of the instrumentation used in these experiments was 0.6 nm-6 μm; therefore, aggregates larger than 6 μm may exist in these solutions.