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Phosphorus transport from agricultural land contributes to eutrophication of surface waters. Pipe drain and trench waters from a grassland field on a heavy clay soil in the Netherlands were sampled before and after manure application. Phosphorus speciation was analyzed by physicochemical P fractionation, and the colloidal P fraction in the dissolved fraction (<0.45 μm) was analyzed by asymmetric flow field-flow fractionation (AF4) coupled to high-resolution inductively coupled plasma-mass spectrometry and ultraviolet diode array detector. When no manure was applied for almost 7 mo, total P (TP) concentrations were low (<21 μmol L), and TP was almost evenly distributed among dissolved reactive P (DRP), dissolved unreactive P (DUP), and particulate P (PP). Total P concentrations increased by a factor of 60 and 4 when rainfall followed shortly after application of cattle slurry or its solid fraction, respectively. Under these conditions, DRP contributed 50% or more to TP. The P speciation within the DUP and PP fractions varied among the different sampling times. Phosphorus associated with dissolved organic matter, probably via cation bridging, comprised a small fraction of DUP at all sampling times. Colloidal P coeluted with clay particles when P application was withheld for almost 7 mo and after application of the solid cattle slurry fraction. At these sampling times, PP correlated well with particulate Fe, Al, and Si, indicating that P is associated with colloidal clay particles. After cattle slurry application, part of DUP was probably present as phospholipids. Physicochemical fractionation combined with AF4 analysis is a promising tool to unravel the speciation of colloidal P in environmental water samples.

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The loss of P in overland flow or leachate from manure patches can impair surface water quality. We studied leaching of P from 10-cm-high lysimeters filled with intact grassland soil or with acid-washed sand. A manure patch was created on two grassland and two sand-filled lysimeters, and an additional two grass lysimeters served as blanks. Lysimeters were leached in the laboratory during 234 d with a diluted salt solution, and column effluent was passed through a 0.45-microm filter, analyzed for pH, dissolved reactive P (DRP), and total dissolved P (TDP). At the end of the experiment lysimeter soil was sampled and analyzed for pH, available P, and oxalate-extractable P, Fe, and Al. The concentration of TDP in the effluent from the sand column increased to 25 mg L-1 during the first weeks and remained above 10 mg L-1 during the rest of the percolation. In effluent from grass + patch lysimeters TDP gradually increased to 4 mg L-1. Both in the manure and in the effluent of the sand lysimeter P was found mainly in the form of DRP, but in the effluent from the grass lysimeters was found mainly as dissolved unreactive P (DUP=TDP-DRP). Earthworm activity was responsible for decomposition of the manure patch on the grass lysimeters. Manure patches and their remains were found to be a long-term source of high concentrations of P in leachates. Spreading of patches after a grazing period could reduce their possible negative impacts on the environment.