An on-line high pressure size exclusion chromatography (HPSEC) with UV and TOC detectors was adapted to examine the distribution of relative molecular mass of natural organic matter (NOM). Through synchronous determination of UV254 and TOC responses in a wide range of relative molecular mass, it was possible to accurately characterize the structure of NOM, especially for some non-aromatic and non-conjugated double bond organics which have low response to UV. It was found that, TOC detector was capable of detecting all kinds of organic matters, including sucrose, sodium alginate and other hydrophilic organic compounds. The sample volume had a positively linear correlation with the TOC response, indicating that the larger volume would produce stronger responses. The effect of ion strength was relatively low, shown by the small decrease of peak area (1.2% ) from none to 0.2 mol x L(-1) NaCl. The pH value of tested samples should be adjusted to neutral or acidic because when the samples were alkaline, the results might be inaccurate. Compared to the sample solvents adopted as ultrapure water, the samples prepared by mobile phase solvents had less interference to salt boundary peak. The on-line HPSEC-UV-TOC can be used accurately to characterize the distribution of relative molecular mass and its four fractions in River Xiang.

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