Global patterns of dissolved N, P and Si in large rivers

The concentration of dissolved inorganic nitrogen (DIN), dissolved nitrate-N, Total-N (TN), dissolved inorganic phosphate (DIP), total phosphorus (TP), dissolved silicate-Si (DSi) and their ratios in the world's largest rivers are examined using a global data base that includes 37% of the earth's watershed area and half its population. These data were compared to water quality in 42 subbasins of the relatively well-monitored Mississippi River basin (MRB) and of 82 small watersheds of the United States. The average total nitrogen concentration varies over three orders of magnitude among both world river watersheds and the MRB, and is primarily dependent on variations in dissolved nitrate concentration, rather than particulate or dissolved organic matter or ammonium. There is also a direct relationship between the DIN:DIP ratio and nitrate concentration. When nitrate-N exceeds 100 g-at l^–1, the DIN:DIP ratio is generally above the Redfield ratio (16:1), which implies phosphorus limitation of phytoplankton growth. Compared to nitrate, the among river variation in the DSi concentration is relatively small so that the DSi loading (mass/area/time) is largely controlled by runoff volume. The well-documented influence of human activities on dissolved inorganic nitrogen loading thus exceeds the influences arising from the great variability in soil types, climate and geography among these watersheds. The DSi:nitrate-N ratio is controlled primarily by nitrogen loading and is shown to be inversely correlated with an index of landscape development – the City Lights nighttime imagery. Increased nitrogen loading is thus driving the world's largest rivers towards a higher DIN:DIP ratio and a lower DSi:DIN ratio. About 7.3 and 21 % of the world's population lives in watersheds with a DSi:nitrate-N ratio near a 1:1 and 2:1 ratio, respectively. The empirical evidence is that this percentage will increase with further economic development. When the DSi:nitrate-N atomic ratio is near 1:1, aquatic food webs leading from diatoms (which require silicate) to fish may be compromised and the frequency or size of harmful or noxious algal blooms may increase. Used together, the DSi:nitrate-N ratio and nitrate-N concentration are useful and robust comparative indicators of eutrophication in large rivers. Finally, we estimate the riverine loading to the ocean for nitrate-N, TN, DIP, TP and DSi to be 16.2, 21, 2.6, 3.7 to 5.6, and 194 Tg yr^–1, respectively.