Ultrafiltration of Nonionic Surfactants and Dissolved Organic Matter

A brownwater sample with a high content of humic substances (HS) was fractionated by multistage ultrafiltration (mst-UF) into five fractions with nominal molecular weights ranging from >30 to <1 kDa. Fractions were characterized with respect to molecular size distribution and structure. Size exclusion chromatography with online DOC detection revealed that mst-UF yielded fractions with decreasing Mp (molecular weight at peak maximum) and polydispersities from nominally large to small mst-UF fractions. 13C MAS NMR analysis showed that the content of carbohydrate structures decreased from the original sample toward smaller molecular weight (MW) fractions, which in turn contained more carboxylic groups and branched aliphatic structures. Specific UV absorbances (SUVA254) were highest in the >30 kDa fraction and decreased with decreasing MW. To evaluate whether separation mechanisms other than size exclusion were of importance during the fractionation, the behavior of low molecular weight model compounds (MC) with a range of polarities was studied. Recoveries decreased with increasing hydrophobicity of the MC. For selected nonylphenol ethoxylates and 4-nonylphenol the recovery correlated well with the hydrophile-lipophile balance value. The presence of dissolved organic matter (DOM) caused an additional loss of hydrophobic MC, possibly because of sorption of the compounds onto DOM fouling layers. The hydrophilic MC caffeine was recovered almost completely (85-86%) regardless of the DOM content of the model solution. It was concluded that size exclusion was the dominant fractionation mechanism for caffeine, whereas hydrophobic interactions played a major role during the mst-UF fractionation of nonpolar contaminants. For a better understanding of the behavior of polyfunctional molecules such as HS, the effect of other physicochemical properties needs to be investigated in further studies.