Aggregation of aquatic humic substances

Humic substances (HS) were isolated from Penwhirn Reservoir (PR) and Esthwaite Water (EW) and their removal from solution by centrifugation was studied as a function of pH, humic concentration and molecular weight, and CaCl₂ concentration. Large amounts (up to 50%) of PR HS could be removed but only small amounts (? 3%) of EW HS. At pH ? 5 removal of PR HS by Ca²⁺ can be explained satisfactorily in terms of decreases in humic solubilities induced by complexation with the cation. However, removal induced by protonation of the PR HS is unusual in that it decreases with increasing humic concentration.The results suggest that PR HS comprise a range of molecules differing in solubility, with the high-molecular-weight (40,000) components being the least soluble. The EW HS consist of molecules of weight-average molecular weight 5000 and resemble similarly sized PR HS in that they remain unaggregated in solution even when highly complexed with Ca²⁺.