Composition, sources, and bioavailability of nitrogen in a longitudinal gradient from freshwater to estuarine waters

Nitrogen (N) transport from land to water is a dominant contributor of N in estuarine waters leading to eutrophication, harmful algal blooms, and hypoxia. Our objectives were to (1) investigate the composition of inorganic and organic N forms, (2) distinguish the sources and biogeochemical mechanisms of nitrate-N (NO₃-N) transport using stable isotopes of NO₃^- and Bayesian mixing model, and (3) determine the dissolved organic N (DON) bioavailability using bioassays in a longitudinal gradient from freshwater to estuarine ecosystem located in the Tampa Bay, Florida, United States. We found that DON was the most dominant N form (mean: 64%, range: 46-83%) followed by particulate organic N (PON, mean: 22%, range: 14-37%), whereas inorganic N forms (NO_x-N: 7%, NH₄-N: 7%) were 14% of total N in freshwater and estuarine waters. Stable isotope data of NO₃^- revealed that nitrification was the main contributor (36.4%), followed by soil and organic N sources (25.5%), NO₃^- fertilizers (22.4%), and NH₄⁺ fertilizers (15.7%). Bioassays showed that 14 to 65% of DON concentrations decreased after 5-days of incubation indicating utilization of DON by microbes in freshwater and estuarine waters. These results suggest that despite low proportion of inorganic N forms, the higher concentrations and bioavailability of DON can be a potential source of N for algae and bacteria leading to water quality degradation in the estuarine waters.