Nutrient inputs to surface waters are particularly varied in urban areas, due to multiple nutrient sources and complex hydrologic pathways. Because of their close proximity to coastal waters, nutrient delivery from many urban areas can have profound impacts on coastal ecology. Relatively little is known about the temporal and spatial variability in stoichiometry of inorganic nutrients such as dissolved silica, nitrogen, and phosphorus (Si, N, and P) and dissolved organic matter in tropical urban environments. We examined nutrient stoichiometry of both inorganic nutrients and organic matter in an urban watershed in Puerto Rico served by municipal sanitary sewers and compared it to two nearby forested catchments using samples collected weekly from each river for 6 yr. Urbanization caused large increases in the concentration and flux of nitrogen and phosphorus (2- to 50-fold), but surprisingly little change in N:P ratio. Concentrations of almost all major ions and dissolved silica were also significantly higher in the urban river than the wildland rivers. Yield of dissolved organic carbon (DOC) was not increased dramatically by urbanization, but the composition of dissolved organic matter shifted toward N-rich material, with a larger increase in dissolved organic nitrogen (DON) than DOC. The molar ratio of DOC:DON was about 40 in rivers draining forested catchments but was only 10 in the urban river. Inclusion of Si in the assessment of urbanization's impacts reveals a large shift in the stoichiometry (Si:N and Si:P) of nutrient inputs. Because both Si concentrations and watershed exports are high in streams and rivers from many humid tropical catchments with siliceous bedrock, even the large increases in N and P exported from urban catchments result in delivery of Si, N, and P to coastal waters in stoichiometric ratios that are well in excess of the Si requirements of marine diatoms. Our data suggest that dissolved Si, often neglected in watershed biogeochemistry, should be included in studies of urban as well as less developed watersheds due to its potential significance for marine and lacustrine productivity.
