Nitrogen cycling in natural waters using in situ, reagentless UV spectrophotometry with simultaneous determination of nitrate and nitrite

Reliable, high temporal, and spatial resolution data is essential for enhancing our understanding of aquatic nitrogen bio-geochemical cycling. This paper describes a novel UV spectrophotometric sensor (ProPS, TriOS GmbH, Oldenburg, Germany) for the real time, in situ, high resolution simultaneous mapping of nitrate/nitrite (linearity 0.01 - 6 mg N L-1, RSD's NO3-N 4-10%, NO2-N 7-14%) in fresh and estuarine waters. Good agreement (t test at p = 0.05) was found with MOOS-1 certified reference material and with reference segmented flow analysis data. River Taw deployments identified a diurnal cycle for NO3-N (0.22-0.63 mg L-1, RSD 3.9%) and for NO2-N (0.01--0.28 mg L-1, RSD 12.4%) with the photo-oxidation of dissolved organic nitrogen a source of diurnal nitrate/nitrite, and a large cyclical amplitude (30-62% of mean nitrate/nitrite). In situ Tamar Estuary nitrate/nitrite concentrations, mapped through the salinity gradient, were strongly correlated with suspended particulate material and inversely correlated with dissolved oxygen and pH, indicating midestuarine, bacterially mediated nitrification/denitrification, with the raised estuarine nitrite also significantly correlated with particulate organic nitrogen. Such previously unquantified inputs have important implications for N loadings calculated from coarse scale sampling and laboratory analysis, pollution assessment, and our understanding of the biological rhythms of aquatic organisms.