Sorption and fractionation of dissolved organic matter and associated phosphorus in agricultural soil

Molibility of dissolved organic matter (DOM) strongly affects the export of nitrogen (N) and phosphorus (P) from oils to surface waters. To study the sorption an mobility of dissolved organic C and P (DOC, DOP) in soil, the pH-dependent sorption of DOM to samples from Ap, EB, and Bt horizons from a Danish agircultural Humic Hapludult was investigated and a kinetic model applicable in field-scale model tested. Sorption experiments of 1 to 72 h duration were conducted at two pH levels (pH 5.0 and 7.0) and six initial DOC concentrtions (0-4.7 mmol L-1). Most sorption/desorption occurred during the first few hours. Dissolved organic carbon and DOP sorption decreased strongly with increased pH and desorption dominated at pH 7, especially for DOC. Due to fractionation during DOM sorption/desorption at DOC concentrations up to 2 mmol L-1, the solution fraction of DOM was enriched in P indicating preferred leaching of DOP. The kinetics of sorption was expressed as a function of how far the solution DOC or DOP concentrations deviate from "equilibrium". The model was able to simulate the kinetics of DOC and DOP sorption/desorption at all concentrations investigated and at both pH levels making it useful for incorporation in field-scale models for quantifying DOC and DOP dynamics

Voltammetric Microsystem for Trace Elements Monitoring

The development of a voltammetric microsystem for monitoring and speciation studies of trace elements in natural waters is presented. This system was designed to provide an efficient coupling of the square-wave anodic stripping voltammetry (SWASV) detection with the permeation liquid membrane (PLM) technique. It consists of a voltammetric microcell, based on a gel-integrated Ir(Hg) microdisk array, a PLM and two micromachined channels for the sample and strip solutions respectively. The analytical performance of the microsystem was first assessed for Pb(II) and Cd(II) and then the simultaneous accumulation and detection of Cd(II), Pb(II) and Cu(II) from a synthetic sample solution was performed. The estimated detection limit of the free metal ion is 2pM for Pb(II) and 75pM for Cd(II) using 5min as deposition time

Integrated micro-analytical system for direct simultaneous voltammetric measurements of free metal ion concentrations in natural waters

A complexing gel integrated microelectrode (CGIME) for direct measurements of free metal ion concentrations in natural waters has been developed. It is prepared by the successive deposition of microlayers of a chelating resin, an antifouling agarose gel and Hg on a 100-interconnected Ir-based microelectrode array. The trace metals of interest are in a first step accumulated on the chelating resin in proportion to their free ion concentration in solution, then released in acidic solution and detected simultaneously by using square wave anodic stripping voltammetry (SWASV). The reliability of this sensor for the simultaneous measurement of copper, lead and cadmium has been studied by a series of replicate laboratory tests. The proportionality between the voltammetric peak current intensity and the free metal ion concentrations in solution has been demonstrated by using malonate as a model ligand. Finally, the CGIME sensor was applied to the Cu and Pb free concentration measurement in sea water samples and the results compared to the free metal ion concentrations measured using hollow fiber based permeation liquid membrane (HF-PLM) coupled to inductively coupled plasma mass spectrophotometer (ICP-MS). Comparable concentration values were found for both metals with both techniques allowing to validate the CGIME measurements in complex media. © 2006 Wiley-VCH Verlag GmbH & Co. KGaA

The chemical speciation of Fe(III) in freshwaters

Dialysis and chemical speciation modelling have been used to calculate activities of Fe3+ for a range of UK surface waters of varying chemistry (pH 4.3–8.0; dissolved organic carbon 1.7–40.3 mg l-1) at 283K. The resulting activities were regressed against pH to give the empirical model: log aFe3+ = 2.76(±0.53) – 2.63(±0.08)•pH Predicted Fe3+ activities are consistent with a solid–solution equilibrium with hydrous ferric oxide. However, the apparent solubility of the solid phase decreases as pH decreases, consistent with some previous studies on Fe(III) solubility in the laboratory. The empirical model was used to predict concentrations of Fe in dialysates and ultrafiltrates of globally distributed surface and soil/ground waters. The predictions were improved greatly by the incorporation of a temperature correction for aFe3+, consistent with the temperature–dependence of previously reported hydrous ferric oxide solubility. The empirical model, incorporating temperature effects, may be used to make generic predictions of the ratio of free and complexed Fe(III) to dissolved organic matter in freshwaters. Comparison of such ratios with observed Fe : dissolved organic matter ratios allows an assessment to be made of the amounts of Fe present as Fe(II) or colloidal Fe(III), where no separate measurements have been made