Fluorescence Verses Radioactivity Labeling for Lab-Scale Investigation of the Fate of Water-Soluble Polymers in Wastewater Treatment Plants

Water-soluble synthetic polymers are extensively used in cosmetics, detergents and paints. Many end up in wastewater and, later on, in wastewater-treatment plants. In order to gain an insight into their fate in such plants, fluorescence and radioactivity labelings were compared using a lab-scale reactor designed to mimic industrial conditions. Two fermentation media were considered, namely a mixture of E402 and E204 micro-organisms and an activated sludge collected from a water-treatment plant located in the south of France. A sample of low molar mass commercial poly(acrylic acid) (PAA) was labeled by radioactivity with tritium and by coupling the 6-aminofluorescein fluorescent dye. Labeled PAA-containing sludges were allowed to ferment. To monitor the fate of the polymers, aliquots of the fermented mixtures were withdrawn at selected times and centrifuged. Liquid and solid phases were analyzed by scintigraphy or UV spectrometry, depending of the labeling techniques. Both techniques led to similar distributions, c.a. 75% in the supernatant and 25% in the solid phase. Distributions remained constant during the biological tests. There was no degradation of the commercial PAA after aqueous size exclusion chromatography (SEC), in agreement with literature. These features showed that fluorescence-labeling can be used instead of the complex and expensive radiolabeling. The validated fluorescence-based method was then applied to a linear poly(acrylic acid) synthesized by ATRP and labeled with 6-aminofluorescein. There was no significant difference between the commercial and the linear poly(acrylic acid)s. In contrast, a linear PAA with 5% of tert-butyl ester repeating units was predominantly found in the solid phase although adsorption or absorption by micro-organisms could not be demonstrated. The method based on fluorescence labeling should be applicable to other water soluble polymers provided that the dye remains attached to the polymer as it was the case for the studied poly(acrylic acid)s.