A Novel In Situ Method for Simultaneously and Selectively Measuring AsIII, SbIII, and SeIV in Freshwater and Soils

Abstract

Anthropogenic and climatic perturbations redistribute arsenic (As), antimony (Sb), and selenium (Se) within the environment. The speciation characteristics of these elements determine their behavior and biogeochemical cycling, but these redox-sensitive species are challenging to capture, with few methods able to harmonize measurements across the whole plant-soil-ecosystem continuum. In this study, we developed a novel diffusive gradient in thin films (DGT) method based on aminopropyl and mercaptopropyl bi-functionalized mesoporous silica spheres (AMBS) to achieve in-situ, simultaneous, and selective quantification of As^III, Sb^III, and Se^IV, three typical/toxic but difficult to measure inorganic species. When used for environmental monitoring within a river catchment, AMBS-DGT exhibited stable/accurate predictions of these species despite varying water chemistries (ionic strength 0.01-200 mmol L^-1 NO₃^-, pH 5-9 for As^III and Sb^III, and pH 5-7.5 for Se^IV). Furthermore, river deployments also showed that time-averaged species concentrations by AMBS-DGT were reproducible compared with high-frequency sampling and measurement by high performance liquid chromatography coupled with inductively coupled plasma mass spectroscopy. When AMBS-DGT was used for sub-mm scale chemical imaging of soil solute fluxes, the method resolved concomitant redox-constrained spatial patterns of As^III, Sb^III, and Se^IV associated with root O₂ penetration within anaerobic soil. Improved capabilities for measurement of compartment interfaces and microniche features are critical alongside the measurement of larger-scale hydrological processes that dictate the fine-scale effects, with the AMBS-DGT achieving this for As^III, Sb^III, and Se^IV.