Physico-chemical factors controlling the speciation of phosphorus in English and Welsh rivers.

Phosphorus is a finite resource essential for global food production. However, excessive loss to river systems from diffuse sources (typically agricultural) and point sources (e.g. waste water treatment works and industrial effluent) can lead to negative environmental impacts, including changes to diatom and invertebrate community structure. Current environmental quality standards for phosphorus in the UK have been based on reactive phosphorus, which is poorly defined and comprises an unknown proportion of soluble reactive phosphorus and chemically extractable particulate phosphorus. This research assesses the influencing factors that may control soluble reactive phosphorus concentrations in rivers, including dissolved iron, as well as partitioning processes associated with the presence of total suspended solids, and questions the reliability of the assumptions used when setting environmental quality standards. The extensive phosphorus speciation monitoring carried out across a wide geographic area of England and Wales shows that not all phosphorus as measured by the molybdenum blue method is either soluble or necessarily bioavailable, particularly at concentrations in the range in which the Environmental Quality Standard for 'Good' status (typically less than 100 µg P L-1) has been set. Phosphorus speciation can change due to physico-chemical processes which vary spatially and/or temporally, including precipitation with iron and partitioning with suspended solids.

A deconvolutional Bayesian mixing model approach for river basin sediment source apportionment.

Increasing complexity in human-environment interactions at multiple watershed scales presents major challenges to sediment source apportionment data acquisition and analysis. Herein, we present a step-change in the application of Bayesian mixing models: Deconvolutional-MixSIAR (D-MIXSIAR) to underpin sustainable management of soil and sediment. This new mixing model approach allows users to directly account for the 'structural hierarchy' of a river basin in terms of sub-watershed distribution. It works by deconvoluting apportionment data derived for multiple nodes along the stream-river network where sources are stratified by sub-watershed. Source and mixture samples were collected from two watersheds that represented (i) a longitudinal mixed agricultural watershed in the south west of England which had a distinct upper and lower zone related to topography and (ii) a distributed mixed agricultural and forested watershed in the mid-hills of Nepal with two distinct sub-watersheds. In the former, geochemical fingerprints were based upon weathering profiles and anthropogenic soil amendments. In the latter compound-specific stable isotope markers based on soil vegetation cover were applied. Mixing model posterior distributions of proportional sediment source contributions differed when sources were pooled across the watersheds (pooled-MixSIAR) compared to those where source terms were stratified by sub-watershed and the outputs deconvoluted (D-MixSIAR). In the first example, the stratified source data and the deconvolutional approach provided greater distinction between pasture and cultivated topsoil source signatures resulting in a different posterior distribution to non-deconvolutional model (conventional approaches over-estimated the contribution of cultivated land to downstream sediment by 2 to 5 times). In the second example, the deconvolutional model elucidated a large input of sediment delivered from a small tributary resulting in differences in the reported contribution of a discrete mixed forest source. Overall D-MixSIAR model posterior distributions had lower (by ca 25-50%) uncertainty and quicker model run times. In both cases, the structured, deconvoluted output cohered more closely with field observations and local knowledge underpinning the need for closer attention to hierarchy in source and mixture terms in river basin source apportionment. Soil erosion and siltation challenge the energy-food-water-environment nexus. This new tool for source apportionment offers wider application across complex environmental systems affected by natural and human-induced change and the lessons learned are relevant to source apportionment applications in other disciplines.

Determining riverine sediment storage mechanisms of biologically reactive phosphorus in situ using DGT.

Phosphorus (P) is the main reason many surficial water bodies in the UK are currently failing to meet the chemical standards set by the Water Framework Directive (WFD). This work focuses on the role of sediments in the upper reaches of the River Taw in the South West of the UK. Point and diffuse sources of P have been identified as well as a number of mitigation measures applied or planned to address the issues. However, it is unknown what effect these sources have had on the river's sediments and how they will react to diminishing inputs of P into the water column in the future. The diffusive gradient in thin-films (DGT) method is utilised in situ to quantify and identify labile, potentially bioavailable P fluxes and potential storage mechanisms at sites of known diffuse and point P inputs. In the vicinity of a heavily contaminated point source, data present here shows that sediments are still acting as a sink. The proposed mechanism for this is the formation of a 'calcium cap' which provides a geochemical barrier between the sediment and overlying water to prevent loss of labile P. The strong correlation between calcium and total P under most circumstances supports this hypothesis. This conclusion provides some confidence that even though P concentrations in some sediments are significantly elevated, mobility between the sediment and overlying water is restricted. In the context of routine monitoring against WFD targets, the molybdenum blue method generally employed to determine soluble reactive phosphorus was shown to not be equivalent to the DGT labile P pool, especially at pristine or moderately point/diffuse influenced sites. This is likely due to desorption of weakly bound P from colloids, which is unavailable to DGT devices. These results have the potential to be scaled up to the full catchment or other catchments which exhibit similar physical and chemical sediment composition and provide a stronger foundation for management and target setting than current monitoring approaches.