Assessment of natural fluorescence as a tracer of diffuse agricultural pollution from slurry apreading on intensely-farmed grasslands

The value of natural fluorescence in tracing diffuse pollution, in liquid phase, following slurry application to land was assessed by field experiment using twelve one hectare lysimeters on a heavy clay soil in Devon, UK, during autumn 2007. A strong linear relationship was found between natural fluorescence intensity and slurry concentration. The ratio of indices of tryptophan-like and fulvic/humic-like fluorescence (TI:FI) varied between 2 and 5 for a range of slurries sampled from Devon farms and allowed slurry to be distinguished from uncontaminated drainage waters (TI:FI < 1). Incidental losses of slurry, indicated by significantly enhanced TI:FI ratios, high TI and high ammonium levels, occurred via the drain flow pathway of the drained lysimeters during the first small event following slurry-spreading. The maximum estimated loss from a single lysimeter was 2-8 kg or 0.004-0.016% of the applied slurry. In the second larger storm event, some five weeks later, significantly enhanced TI:FI ratios in the drain flows were not associated with high TI but with high nitrate levels and, compared to the earlier storm, an increase in the humification index. This implies the loss of slurry decomposition products during this event but further work is needed to validate this. There was no significant enhancement of TI:FI in the surface/throughflow pathways of the drained or undrained lysimeters in either of the events. The observed change over a period of weeks in the strength and nature of the fluorescence signal from spread slurry restricts quantification of slurry losses to those immediately after slurry spreading. Nonetheless, this study demonstrates the utility of fluorescence as an indicator of slurry in drainage waters and the importance of field drains in diffuse agricultural pollution

Effects of storm events on mobilisaton and in-stream processing of dissolved organic matter (DOM) in a Welsh peatland catchment.

Peatlands are important contributors of dissolved organic matter (DOM) to downstream aquatic systems. We investigated the effects of storm events on dissolved organic carbon (DOC) concentrations and DOM quality in a stream draining a Welsh peatland catchment. Intensive stream samples were collected and analysed for pH, DOC, dissolved organic nitrogen (DON), absorbance and fluorescence. Soil water samples and samples of sphagnum pore water were also collected, and a simple end-member mixing model was applied to account for changes occurring during the events. Fluorescence data were interpreted using parallel factor analysis (PARAFAC). DOC concentrations increased and pH decreased during the storm events. The soil water data and the mixing model indicated that this was due to a change of flow paths and draining of the DOC-rich acrotelm. Absorbance indices and the DOC/DON ratio suggested that the DOM released during events was less degraded. There was a striking, inversely related diurnal pattern in absorbance and fluorescence after the discharge peak. The diurnal pattern and a lack of fit with the mixing model suggested that fluorescing DOM was mainly produced in-stream. Fluorescence has been found to peak in the morning and decline during day-time due to photo-bleaching. We hypothesise that the input of additional DOM during events causes a change in the diurnal pattern, giving a peak at mid-day, when the processing of the additional DOM is highest