On-line dynamic fractionation and automatic determination of inorganic phosphorus in environmental solid substrates exploiting sequential injection microcolumn extraction and flow injection analysis.

Sequential injection microcolumn extraction (SI-MCE) based on the implementation of a soil-containing microcartridge as external reactor in a sequential injection network is, for the first time, proposed for dynamic fractionation of macronutrients in environmental solids, as exemplified by the partitioning of inorganic phosphorus in agricultural soils. The on-line fractionation method capitalises on the accurate metering and sequential exposure of the various extractants to the solid sample by application of programmable flow as precisely coordinated by a syringe pump. Three different soil phase associations for phosphorus, that is, exchangeable, Al- and Fe-bound, and Ca-bound fractions, were elucidated by accommodation in the flow manifold of the three steps of the Hieltjes-Lijklema (HL) scheme involving the use of 1.0M NH4Cl, 0.1M NaOH and 0.5M HCl, respectively, as sequential leaching reagents. The precise timing and versatility of SI for tailoring various operational extraction modes were utilized for investigating the extractability and the extent of phosphorus re-distribution for variable partitioning times. Automatic spectrophotometric determination of soluble reactive phosphorus in soil extracts was performed by a flow injection (FI) analyser based on the Molybdenum Blue (MB) chemistry. The 3sigma detection limit was 0.02 mg P L(-1) while the linear dynamic range extended up to 20 mg P L(-1) regardless of the extracting media. Despite the variable chemical composition of the HL extracts, a single FI set-up was assembled with no need for either manifold re-configuration or modification of chemical composition of reagents. The mobilization of trace elements, such as Cd, often present in grazed pastures as a result of the application of phosphate fertilizers, was also explored in the HL fractions by electrothermal atomic absorption spectrometry.