In Situ Selective Measurement Based on Diffusive Gradients in Thin Films Technique with Mercapto-Functionalized...

In situ monitoring of Sb speciation improves the understanding of Sb biogeochemistry and toxicity in ecosystems. Precise measurement of Sb is a challenge due to its instability of oxidation and ultratrace concentration. The development of simple and reliable methods specific to Sb^III measurement is not only appealing but essential for implementing regulations. Here, we present an in situ speciation analysis method for Sb^III, using the diffusive gradients in thin films (DGT) technique, combined with mercapto-functionalized SBA-15 mesoporous silica nanoparticles (MSBA). Laboratory performance tests confirmed MSBA-DGT uptake was independent of pH (4-9) and ionic strength (0.1-200 mmol L^-1). DGT devices equipped with MSBA-based binding gels showed a theoretically linear accumulation of Sb^III and exhibited a high capacity for Sb^III at 65 μg/gel disc, with negligible accumulation of Sb^V over a 72 h deployment. Compared with commercial 3-mercaptopropyl-functionalized silica (MFS), the nanosized MSBA facilitate its even distribution in the binding gels. Furthermore, the good selectivity and high homogeneity of the MSBA gel enabled it to be applied in a rice rhizosphere in conjunction with AgI gel to investigate the effects of sulfur application on the Sb^III solubility. In summary, the newly developed MSBA-DGT provides a selective measurement of Sb^III, showing potential for environmental monitoring and further application in understanding the biogeochemical process of Sb.