Contrasting controls on the phosphorus concentration of suspended particulate matter under baseflow and storm event conditions in agricultural headwater streams

Whilst the processes involved in the cycling of dissolved phosphorus (P) in rivers have been extensively studied, less is known about the mechanisms controlling particulate P concentrations during small and large flows. This deficiency is addressed through an analysis of large numbers of suspended particulate matter (SPM) samples collected under baseflow (n=222) and storm event (n=721) conditions over a 23-month period across three agricultural headwater catchments of the River Wensum, UK. Relationships between clay mineral and metal oxyhydroxide associated elements were assessed and multiple linear regression models for the prediction of SPM P concentration under baseflow and storm event conditions were formulated. These models, which explained 71-96% of the variation in SPM P concentration, revealed a pronounced shift in P association from iron (Fe) dominated during baseflow conditions to particulate organic carbon (POC) dominated during storm events. It is hypothesised this pronounced transition in P control mechanism, which is consistent across the three study catchments, is driven by changes in SPM source area under differing hydrological conditions. In particular, changes in SPM Fe-P ratios between small and large flows suggest there are three distinct sources of SPM Fe; surface soils, subsurface sediments and streambed iron sulphide. Further examination of weekly baseflow data also revealed seasonality in the Fe-P and aluminium oxalate-dithionate (Alox-Aldi) ratios of SPM, indicating temporal variability in sediment P sorption capacity. The results presented here significantly enhance our understanding of SPM P associations with soil derived organic and inorganic fractions under different flow regimes and has implications for the mitigation of P originating from different sources in agricultural catchments.