Characterization of the perylenequinone pigments in Japanese andosols and cambisol

The green fraction of humic acid (Pg) and the chloroform-extractable green fraction (CEGF) are characteristic soil organic matter (SOM) components. These alkaline solutions are green-colored due to the presence of 4,9-dihydroxyperylene-3,10-quinone (DHPQ) chromophore. While both of which are potential indicators for the effect of land use and paleoclimatic environment in the fields of soil science as well as geochemistry, CEGF as well as its relationship with Pg in soils are not yet fully documented. In this study, we firstly investigated the chemical properties of soil CEGF fractions by ultraviolet-visible (UV-Vis) and infrared (IR) method. Two CEGF components were separated by sequential liquid-liquid extraction using aqueous ammonium hydroxide (NH4OH) followed by aqueous sodium hydroxide (NaOH). Results showed that the UV-Vis spectral shape of NH4OH-extractable component is very similar to that of DHPQ, except that it is red-shifted. The solubility and UV-Vis spectrum of the NaOH-extractable fraction were completely identical with those of synthesized DHPQ. Their IR spectral shapes were also almost the same. Subsequently, the distribution of CEGF in humic acid (HA), fulvic acid (FA) and humin (HN) from Japanese Andosols and Cambisol was quantitatively evaluated by sequential extraction. Most of CEGF was detected in the HA (60-78%) and HN (22-40%), but not in the FA. While the UV-Vis spectral shape of CEGF extracted from Andosols HAs showed a relatively higher proportion of DHPQ than its derivative, the opposite was observed in Cambisol HA, whose CEGF is similar to that of sclerotium grain (one of the possible origin of CEGF). These results suggest the diversity of CEGF-producing soil fungi. Quantitative data also indicated that 35-49% of Pg consisted of a chloroform-soluble fraction (i.e., CEGF) and the remaining 51-65% of Pg was chloroform-insoluble. Based on these results, we propose that CEGF is composed of DHPQ and DHPQ-derivatives and that CEGF is one of the major fractions of Pg.