Online Microdialysis-High-Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry...

Conventional soil solution sampling of species-sensitive inorganic contaminants, such as hexavalent chromium (Cr^VI), may induce interconversions due to disruption of system equilibrium. The temporal resolution that these sampling methods afford may also be insufficient to capture dynamic interactions or require time-consuming and expensive analysis. Microdialysis (MD) is emerging as a minimally invasive passive sampling method in environmental science, permitting the determination of solute fluxes and concentrations at previously unobtainable spatial scales and time frames. This article presents the first use of MD coupled to high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) for the continuous sampling and simultaneous detection of Cr^VI in soil solution. The performance criteria of the system were assessed using stirred solutions; good repeatability of measurement (RSD < 2.5%) was obtained for Cr^VI, with a detection limit of 0.2 μg L^-1. The online MD-HPLC-ICP-MS setup was applied to the sampling of native Cr^VI in three soils with differing geochemical properties. The system sampled and analyzed fresh soil solution at 15 min intervals, offering improved temporal resolution and a significant reduction in analysis time over offline MD. Simple modifications to the chromatographic conditions could resolve additional analytes, offering a powerful tool for the study of solute fluxes in soil systems to inform research into nutrient availability or soil-to-plant transfer of potentially harmful elements.