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A six-month series of high-resolution synchronous stream discharge and total phosphorus (TP) concentration data is presented from a 5 km 2 agricultural catchment in the Lough Neagh basin, Northern Ireland. The data are hourly averages of 10-minute measurements using a new bankside, automatic, continuous monitoring technology. Three TP transfer event-types occur in this catchment: (1) chronic, storm independent transfers; (2) acute, storm dependent transfers; (3) acute, storm independent transfers. Event-type 2 transferred over 90% of the total 279 kg TP load in 39% of the total period; it corresponded to diffuse transfers from agricultural soils. Event-types 1 and 3, however, maintained the river in a highly eutrophic state between storm events and were characteristic of point source pollution, despite there being no major industrial or municipal point sources. Managing P transfers at the catchment scale requires a robust monitoring technology to differentiate between dynamic, multiple sources and associated event types and so enable a reliable assessment of the performance of mitigation measures, monitored at catchment outlets. The synchronous and continuous TP and discharge data series generated in this study demonstrate how this is possible.

Recent technological breakthroughs of optical sensors and analysers have enabled matching the water quality measurement interval to the time scales of stream flow changes and led to an improved understanding of spatially and temporally heterogeneous sources and delivery pathways for many solutes and particulates. This new ability to match the chemograph with the hydrograph has promoted renewed interest in the concentration-discharge (c-q) relationship and its value in characterizing catchment storage, time lags and legacy effects for both weathering products and anthropogenic pollutants. In this paper we evaluated the stream c-q relationships for a number of water quality determinands (phosphorus, suspended sediments, nitrogen) in intensively managed agricultural catchments based on both high-frequency (sub-hourly) and long-term low-frequency (fortnightly-monthly) routine monitoring data. We used resampled high-frequency data to test the uncertainty in water quality parameters (e.g. mean, 95th percentile and load) derived from low-frequency sub-datasets. We showed that the uncertainty in water quality parameters increases with reduced sampling frequency as a function of the c-q slope. We also showed that different sources and delivery pathways control c-q relationship for different solutes and particulates. Secondly, we evaluated the variation in c-q slopes derived from the long-term low-frequency data for different determinands and catchments and showed strong chemostatic behaviour for phosphorus and nitrogen due to saturation and agricultural legacy effects. The c-q slope analysis can provide an effective tool to evaluate the current monitoring networks and the effectiveness of water management interventions. This research highlights how improved understanding of solute and particulate dynamics obtained with optical sensors and analysers can be used to understand patterns in long-term water quality time series, reduce the uncertainty in the monitoring data and to manage eutrophication in agricultural catchments.

High-resolution measurements of total phosphorus (TP) concentrations in a stream draining a 5 km 2 agricultural catchment (a sub-catchment of Lough Neagh in Northern Ireland) were made every 10 mins by continuous flow instrumentation using new homogenisation, digestion and colorimetric phases. Concurrently, rainfall and stream discharge data were collected at 5 and 15 min. intervals. Major P flushing episodes during storm events peaked on the rising limbs of storm hydrographs. A period of baseflow also indicated the importance of other sources that maintain the stream in a eutrophic state between storm events. These data provide insights into catchment processes that conform to definite patterns that, in a coarser sampling regime, might ordinarily be attributed to sampling and analytical noise.

of the mechanisms and processes associated with the identification of critical source areas, P mobilization, delivery and biogeochemical processing, as otherwise even highintensity and high-resolution research efforts will only reveal an incomplete picture of the full global impact of the terrestrial derived P on downstream aquatic and marine ecosystems.