Dissolved organic nitrogen (DON) can be a significant part of the reactive N in aquatic ecosystems and can accelerate eutrophication and harmful algal blooms. A bioassay method was coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to determine the biodegradability and molecular composition of DON in the urban stormwater runoff and outflow water from an urban stormwater retention pond. The biodegradability of DON increased from 10% in the stormwater runoff to 40% in the pond outflow water and DON was less aromatic and had lower overall molecular weight in the pond outflow water than in the stormwater runoff. More than 1227 N-bearing organic formulas were identified with FT-ICR-MS in the stormwater runoff and pond outflow water, which were only 13% different in runoff and outflow water. These molecular formulas represented a wide range of biomolecules such as lipids, proteins, amino sugars, lignins, and tannins in DON from runoff and pond outflow water. This work implies that the urban infrastructure (i.e., stormwater retention ponds) has the potential to influence biogeochemical processes in downstream water bodies because retention ponds are often a junction between the natural and the built environment.

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A portion of the dissolved organic nitrogen (DON) is biodegradable in water bodies, yet our knowledge of the molecular composition and controls on biological reactivity of DON is limited. Our objective was to investigate the biodegradability and molecular composition of DON in streams that drain a gradient of 19-83% urban land use. Weekly sampling over 21 weeks suggested no significant relationship between urban land use and DON concentration. We then selected two streams that drain 28% and 83% urban land use to determine the biodegradability and molecular composition of the DON by coupling 5-day bioassay experiments with high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Both urban streams contained a wide range of N-bearing biomolecular formulas and had >80% DON in lignin-like compounds, with only 5-7% labile DON. The labile DON consisted mostly of lipid-and protein-like structures with high H/C and low O/C values. Comparison of reactive formulas and formed counterparts during the bioassay experiments indicated a shift toward more oxygenated and less saturated N-bearing DON formulas due to the microbial degradation. Although there was a little net removal (5-7%) of organic-bound N over the 5-day bioassay, there was some change to the carbon skeleton of DON compounds. These results suggest that DON in urban streams contains a complex mixture of compounds such as lipids, proteins, and lignins of variable chemical structures and biodegradability.

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Stormwater runoff is a leading cause of nitrogen (N) transport to water bodies and hence one means of water quality deterioration. Stormwater runoff was monitored in an urban residential catchment (drainage area: 3.89 hectares) in Florida, United States to investigate the concentrations, forms, and sources of N. Runoff samples were collected over 22 storm events (May to September 2016) at the end of a stormwater pipe that delivers runoff from the catchment to the stormwater pond. Various N forms such as ammonium (NH 4-N), nitrate (NO x-N), dissolved organic nitrogen (DON), and particulate organic nitrogen (PON) were determined and isotopic characterization tools were used to infer sources of NO 3-N and PON in collected runoff samples. The DON was the dominant N form in runoff (47%) followed by PON (22%), NO x-N (17%), and NH 4-N (14%). Three N forms (NO x-N, NH 4-N, and PON) were positively correlated with total rainfall and antecedent dry period, suggesting longer dry periods and higher rainfall amounts are significant drivers for transport of these N forms. Whereas DON was positively correlated to only rainfall intensity indicating that higher intensity rain may flush out DON from soils and cause leaching of DON from particulates present in the residential catchment. We discovered, using stable isotopes of NO 3-, a shifting pattern of NO 3 sources from atmospheric deposition to inorganic N fertilizers in events with higher and longer duration of rainfall. The stable isotopes of PON confirmed that plant material (oak detritus, grass clippings) were the primary sources of PON in stormwater runoff. Our results demonstrate that practices targeting both inorganic and organic N are needed to control N transport from residential catchments to receiving waters.

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