Dissolved humic substances of the Amazon River system 1

Aquatic humic and fulvic acids from nine mainstem and seven major tributary sites in the Amazon River Basin are characterized by their elemental and lignin phenol compositions. Combined humic substances represent 60% of the riverine dissolved organic carbon (DOC), with fulvic to humic acid (FA : HA) ratios in the mainstem averaging 4.7±1.0. All dissolved humic and fulvic acids have clearly recognizable lignin components at levels (8 and 3% of the carbon) suggesting a predominantly allochthonous source. Lignin compositional characteristics are dominated by diagenetic transformations, which include preferential loss of methoxylated structural units and oxidative degradation of lignin side chains. Fulvic acids have consistently lower lignin levels, lower lignin phenol methoxylation, higher acid : aldehyde ratios, and higher C: N ratios than coexisting humic acids, all indicative of greater aerobic degradation of the fulvic acid fraction. An extreme example of lignin degradation is seen in the Rio Negro humic and fulvic acids, which differ significantly in lignin and elemental compositions from other blackwater tributary and mainstem samples. Over most of the mainstem humic and fulvic acids behave conservatively. However, downstream of the Rio Negro confluence, humic acids appear to be selectively adsorbed onto fine suspended particles. Approximately 25 and 40% of the total fluxes of lignin and of carbon are represented in the dissolved humic substances. The annual flux of dissolved, chemically recognizable lignin in the Amazon River at Obidos is calculated to be 1.2 × 10 11 g yr −1 .