Concerted diurnal patterns in riverine nutrient concentrations and physical conditions

Several long-term sets of hourly nitrate concentration data were obtained through deployment of a nitrate sensor in an upper reach of the River Taw, a small moorland-fed river in the South West of the UK. Examination of the data obtained during periods of low flow and the absence of rainfall in the catchment revealed the presence of marked diurnal cycles, which were in concert and negatively correlated with diurnal cycles in water temperature. After verifying that these cycles were natural, an intensive 90-h field monitoring campaign was conducted, in which river water was sampled hourly and immediately analysed in the laboratory for molybdate-reactive phosphorus (P), nitrate, nitrite, ammonium, and pH. Coincident measurements of water temperature, river discharge and solar energy were also taken at, or close to, the site. All measurements revealed diurnal patterns and all patterns were concerted. The cycles of P, nitrate, nitrite, and discharge had two maxima and minima per 24 h, while the cycle of water temperature had one, with a maximum at 20.00 and a minimum at 08.00. The amplitudes of the cycles of P and nitrate were each about 30% of the mean values, while the amplitude of the nitrite cycle was as great as 80% of the mean value on occasions. Both biological and physical mechanisms for the cycling could operate through water temperature and/or incident radiation to account for the observed phenomenon, but there remains uncertainty of which is the more important. The observations have important implications for both the accuracy of pollution assessment in rivers and the physiological rhythms of riverine organisms.