Phosphorus Bioavailability and Speciation dynamics within fluvial suspended sediments

Eutrophication of agricultural catchment streams remains a global problem despite increasingly stringent regulations. Long term, sustained release of bioavailable phosphorus (P) from legacy P stored in fluvial sediments may impact downstream water quality, hence greater understanding is required regarding P speciation dynamics and potential release mechanisms from fluvial sediments to the water column.

This study examined the dynamic P fractions, speciation and bioavailability of suspended fluvial sediments from two geologically contrasting agricultural catchment streams (Ballyboughal (BB) and Tintern Abbey (TTA)) using a combination of complimentary techniques including sequential chemical  fractionations (SCF), Dual Culture Diffusion Apparatus mesocosm experiments (DCDA), X-ray fluorescence spectroscopy (XRF) and X-ray Absorption Near-edge Structure (XANES) spectroscopy. Results from the SCF of fluvial suspended sediments pre- and post DCDA microcosm experiment’s revealed that loosely bound P (P_H2O), exchangeable P against OH^– ions (P_NaOH), and organic P (P_Org) are the major P fraction contributors to the bioavailable P fraction which would promote algal growth. Other P fractions including acid-soluble P principally associated with calcium phosphate compounds (P_HCl) and ferric bound P (P_CBD) showed relatively lower mineralisation to bioavailable P. Significantly, P K-edge XANES spectra enabled identification of seasonal and spatial P speciation dynamics and the existence of major P fractions including Fe-P and Ca-P associated mineral phases along with organic P compounds. Additionally, SCF, XRF and Ca K-edge XANES show contrasting Ca associated phases between both catchments, with calcite dominant in the BB sediments and Ca humic-complexes predominant in the TTA sediments. Contrasting Ca-P fraction transformation mechanisms of the two catchments are indicated by P redistributions in SCF and the reduction of elemental Ca amounts from XRF analysis. Calcium (Ca) K-edge XANES shows the BB catchment has a large amount of calcite while TTA was shown to contain organic Ca compounds, likely in the form of Ca-humic-complexes. This study provides a conjunctive method for future studies and validation of P speciation and bioavailability assessment associated with fluvial suspended sediments from agricultural catchments streams. The results contribute to future catchment scale sedimentary fluvial P modelling and enhanced catchment management strategies to improved water quality.