The chemical composition of water-soluble organic carbon (WSOC) in atmospheric aerosol particles is largely unexplored, due to the myriad of individual compounds, which has hampered attempts to attain a full characterization at the molecular level. An alternative approach, focusing on the analysis of a few main chemical classes, allowed the quantitative fractionation of WSOC into neutral compounds (NC), mono- and di-acids (MDA) and polyacids (PA) through an anion-exchange liquid chromatographic method. Previous attempts to quantify NC, MDA and PA relied on a low-pressure chromatographic technique using a volatile buffer, followed by total organic carbon (TOC) analysis of the fractions, or alternatively on a faster HPLC-UV method which provided a quantification of the fractions based on empirical relationships between UV signal and TOC concentration. Here, we report an upgraded anion-exchange HPLC technique, allowing direct TOC analysis of the eluted fractions, without any pre-treatment, thus permitting a great simplification of quantitative analysis and preventing sample losses. The new HPLC-TOC methodology, employing completely inorganic eluents shows the same efficiency of the former HPLC-UV method employing organic additives, with the exception of phenolic compounds, which are retained on the column by secondary interactions, and low-molecular weight tricarboxylic acids, which are recovered among MDA. The new anion-exchange liquid chromatographic method can recover a substantial amount (86-100%) of water-soluble organic carbon from atmospheric aerosol extracts, thus allowing a higher retention and fractionation capacity with respect to alternative techniques, like solid phase extraction. © 2007 Elsevier B.V. All rights reserved.

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