Investigating the Fe⁰/H₂O systems using the methylene blue method: Validity, applications, and future directions

An innovative approach to characterize the reactivity of metallic iron (Fe⁰) for aqueous contaminant removal has been in use for a decade: The methylene blue method (MB method). The approach considers the differential adsorptive affinity of methylene blue (MB) for sand and iron oxides. The MB method characterizes MB discoloration by sand as it is progressively coated by in-situ generated iron corrosion products (FeCPs) to deduce the extent of iron corrosion. The MB method is a semi-quantitative tool that has successfully clarified some contradicting reports on the Fe⁰/H₂O system. Moreover, it has the potential to serve as a powerful tool for routine tests in the Fe⁰ remediation industry, including quality assurance and quality control (QA/QC). However, MB is widely used as a 'molecular probe' to characterize the Fe⁰/H₂O system, for instance for wastewater treatment. Thus, there is scope to avoid confusion created by the multiple uses of MB in Fe⁰/H₂O systems. The present communication aims at filling this gap by presenting the science of the MB method, and its application and limitations. It is concluded that the MB method is very suitable for Fe⁰ material screening and optimization of operational designs. However, the MB method only provides semi-quantitative information, but gives no data on the solid-phase characterization of solid Fe⁰ and its reaction products. In other words, further comprehensive investigations with microscopic and spectroscopic surface and solid-state analyses are needed to complement results from the MB method.