Constraining the fate of dissolved organic matter (DOM) delivered by rivers is a key to understand the global carbon cycle, since DOM mineralization directly influences air-sea CO 2 exchange and multiple biogeochemical processes. The Amazon River exports large amounts of DOM, and yet the fate of this material in the ocean remains unclear. Here we investigate the molecular composition and transformations of DOM in the Amazon River-ocean continuum using ultrahigh resolution mass spectrometry and geochemical and biological tracers. We show that there is a strong gradient in source and composition of DOM along the continuum, and that dilution of riverine DOM in the ocean is the dominant pattern of variability in the system. Alterations in DOM composition are observed in the plume associated with the addition of new organic compounds by phytoplankton and with bacterial and photochemical transformations. The relative importance of each of these drivers varies spatially and is modulated by seasonal variations in river discharge and ocean circulation. We further show that a large fraction (50-76%) of the Amazon River DOM is surprisingly stable in the coastal ocean. This results in a globally significant river plume with a strong terrigenous signature and in substantial export of terrestrially derived organic carbon from the continental margin, where it can be entrained in the large-scale circulation and potentially contribute to the long-term storage of terrigenous production and to the recalcitrant carbon pool found in the deep ocean.

An Advanced Laser Fluorometer (ALF) capable of discriminating several phytoplankton pigment types was utilized in conjunction with microscopic data to map the distribution of phytoplankton communities in the Amazon River plume in May-June-2010, when discharge from the river was at its peak. Cluster analysis and Non-metric Multi-Dimensional Scaling (NMDS) helped distinguish three distinct biological communities that separated largely on the basis of salinity gradients across the plume. These three communities included an ''estuarine type'' comprised of a high biomass mixed population of diatoms, cryptophytes and green-water Synechococcus spp. located upstream of the plume, a ''mesohaline type'' made up largely of communities of Diatom-Diazotroph Associations (DDAs) and located in the northwestern region of the plume and an ''oceanic type'' in the oligotrophic waters outside of the plume made up of Trichodesmium and Synechococcus spp. Although salinity appeared to have a substantial influence on the distribution of different phytoplankton groups, ALF and microscopic measurements examined in the context of the hydro-chemical environment of the river plume, helped establish that the phytoplankton community structure and distribution were strongly controlled by inorganic nitrate plus nitrite (NO 3 + NO 2) availability whose concentrations were low throughout the plume. Towards the southern, low-salinity region of the plume, NO 3 + NO 2 supplied by the onshore flow of subsurface ($80 m depth) water, ensured the continuous sustenance of the mixed phytoplankton bloom. The large drawdown of SiO 3 and PO 4 associated with this ''estuarine type'' mixed bloom at a magnitude comparable to that observed for DDAs in the mesohaline waters, leads us to contend that, diatoms, cryptophytes and Synechococcus spp., fueled by the offshore influx of nutrients also play an important role in the cycling of nutrients in the Amazon River plume.

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