High frequency measurement of nitrate concentration in the Lower Mississippi River, USA

- Present a 3-year nitrate concentration data with high resolution in a large river.
- NO3 concentrations show minor diurnal variations but consistent seasonal changes.
- Seasonal changes are attributed to hydrology and primary tributary mixing.
- Flux calculations suggest current USGS methods overestimate nitrate loads.
- Information on tributary inputs is needed for NO3 flux estimation in large rivers.

SummaryNutrient concentrations in the Mississippi River have increased dramatically since the 1950s, and high frequency measurements on nitrate concentration are required for accurate load estimations and examinations on nitrate transport and transformation processes. This three year record of high temporal resolution (every 2-3 h) data clearly illustrates the importance of high frequency sampling in improving load estimates and resolving variations in nitrate concentration with river flow and tributary inputs. Our results showed large short-term (days to weeks) variations in nitrate concentration but with no diurnal patterns. A repeatable and pronounced seasonal pattern of nitrate concentration was observed, and showed gradual increases from the lowest values in September (during base-flow), to the highest in June - which was followed by a rapid decrease. This seasonal pattern was only moderately linked with water discharge, and more controlled by nitrogen transformation/export from watershed as well as mixing patterns of the two primary tributaries (the upper Mississippi and the Ohio Rivers), which have distinctly different nitrate concentrations and flow patterns. Based on continuous in situ flow measurements, we estimated 554-886 × 106 kg of nitrate-N was exported from the Mississippi River system during years 2004-2006, which was <9% and <16% lower than U.S. Geological Survey's (USGS) estimates using their LOADEST or composite methods, respectively. USGS methods generally overestimated nitrate loads during rising stages and underestimated the loads during falling stages. While changes in nitrate concentrations in large rivers are generally not as responsive to alterations in diurnal inputs and/or watershed hydrology as small rivers, high-frequency water quality sampling would help in monitoring short-term (days to weeks) variations in nutrient concentration patterns and thus improve the accuracy of nutrient flux estimates.