Temporal variability in sources of dissolved organic carbon in the lower Mississippi River

Here we report on the temporal changes in the composition of dissolved organic carbon (DOC) collected in the tidal freshwater region of the lower Mississippi River. Lignin-phenols, bulk stable carbon isotopes, compound-specific isotope analyses (CSIA) and C-13 nuclear magnetic resonance (NMR) spectrometry were used to examine the composition of high molecular weight dissolved organic matter (HMW DOM) at one station in the lower river over 6 different flow regimes in 1998 and 1999. It was estimated that the annual input of DOC delivered to the Gulf of Mexico from the Mississippi River was of 3.1 X 10(-3) Pg, which represents 1.2% of the total global input of DOC from rivers to the ocean. Average DOC and HMW DOC were 489 +/- 163 and 115 +/- 47 muM, respectively. C-13-NMR spectra revealed considerably more aliphatic structures than aromatic carbons in HMW DOC. Lignin phenols were significantly C-13-depleted with respect to bulk HMW DOM indicating that C-4 grass inputs to the HMW DOM were not significant. It is speculated that C-4 organic matter in the river is not being converted (via microbial decay) to HMW DOM as readily as C-3 organic matter is, because of the association of C-4 organic matter with finer sediments. The predominantly aliphatic C-13 NMR signature of HMW DOM suggests that autochthonous production in the river may be more important as a source of DOC than previously thought. Increases in nutrient loading and decreases in the suspended load (because of dams) in the Mississippi River, as well as other large rivers around the world, has resulted in significant changes in the sources and overall cycling of riverine DOC. Copyright (C) 2004 Elsevier Ltd.