Abstract

The FA and HA fractions represent 20 to 50% of the DOC of the original samples, depending on the origin, and serve as reference materials. The original aqueous samples and the aqueous solutions of the reference materials were characterized with methods suited for measuring samples at natural concentrations. The DOC normalized values of the spectral absorbances (λ = 254 nm; λ = 436 nm) in the original water samples were highest for the brown water and brown coal water and lowest for the secondary effluents. The FA fractions were similar in the UV-absorbance with the exception of the low-absorbing groundwater FA, reflecting a low density of double bonds. The DOC-normalized proton capacity of the FA fractions (10 to 20 μmol/mg) was highest for the brown coal, brown water, and soil-derived samples and again lowest for the groundwater FA. The high values are due to a higher contribution of the weak acids of phenolic type. Specific data for copper complexation capacity (0.5 to 2.5 μmol/mg) went parallel to the proton capacity. The characterization of the FAs by gel chromatography with organic carbon detection revealed three major fractions. The refractory part at short retention time dominated in the brown water and soil-derived samples, whereas the fractions for the lower molecular mass acids at long retention times were dominant in the secondary effluent and the brown coal isolate. Comparison with UV-detected chromatograms revealed a strong decrease in the specific absorbance of the secondary effluent. Up to 3% of the total mass of the FAs could be identified as hydrolyzable amino acids with the highest yield in the sample from secondary effluent and the lowest one in the groundwater sample. The nitrogen content was always higher in the FAs compared to the HAs of the same origin. The application of gel chromatography fluorescence and fluorescence decay time distribution analysis turned out to be a useful tool to differentiate between the different fractions of NOM, the isolates obtained by different methods (e.g., XAD-8, membrane separation) and the fractions of the samples from different origin and age. This is of special value, for the information can also be obtained for samples with natural NOM concentrations, even though further investigations required for full understanding of the data. This work is part of a multi-disciplinary research program (ROSIG: Refraktäre Organische Säuren in Gewässern), funded by the German Research Association (DFG).

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