In Situ Selective Measurement of Se^IV in Waters and Soils: Diffusive Gradients in Thin-Films with Bi-Functionalized...

The speciation of selenium (Se) controls its fate and behavior, determining both its biological and environmental activities. However, in situ monitoring of Se^IV presents a significant challenge due to its sensitivity to redox change. A novel diffusive gradients in thin films (DGT) technique containing mercapto-, amino-bifunctionalized SBA15 mesoporous silica nanoparticles was developed and evaluated in a series of laboratory and field deployment tests. The SBA-DGT exhibited a linear accumulation of Se^IV ( r² > 0.997) over a 72 h deployment, with negligible accumulation of Se^VI(<5%). Consistent prediction of Se^IV occurred within ionic strength and pH ranges of 0.1-200 mmol L^-1 and 3.6-8, respectively. Limits of detection of the SBA-DGT were 0.03 μg Se^IV L^-1, which is suitable for natural waters. Moreover, the properties of the bifunctionalized SBA15 enable it to be fabricated within ultrathin (0.05 mm) gel layers for use in conjunction with O₂ planar optode imaging. This new sandwich sensor technology with SBA-DGT was validated by mapping the two-dimensional distribution of Se^IV and oxygen simultaneously in rice rhizospheres. This study shows that SBA-DGT provides a selective measurement of Se^IV in situ, demonstrating its potential for both environmental monitoring and as a research tool for improving our understanding of Se biogeochemical processes.