Speciation of water soluble iron in size segregated airborne particulate matter using LED based liquid waveguide with a novel dispersive absorption spectroscopic measurement technique

In this study, we present the development and evaluation of a dispersive absorption spectroscopic technique for trace level soluble ferrous detection. The technique makes use of the broadband absorption spectra of the ferrous-ferrozine complex with a novel spectral fitting algorithm to determine soluble ferrous concentrations in samples and achieves much improved measurement precision compared to conventional methods. The developed method was evaluated by both model simulations and experimental investigations. The results demonstrated the robustness of the method against the spectral fluctuation, wavelength drift and electronic noise, while achieving excellent linearity (R² > 0.999) and low detection limit (0.06 μg L⁻¹) for soluble ferrous detection. The developed method was also used for the speciation of soluble iron in size segregated atmospheric aerosols. The measurement was carried out during Spring and Summer in typical urban environment in Hong Kong. The measured total iron concentrations are in good agreement compared to conventional Inductively Coupled Plasma – Optical Emission Spectroscopy (ICP-OES) measurements. Investigation on ambient particulate matter samples shows the size dependent characteristic of iron speciation in the atmosphere with a more active role of fine particles in transforming between ferrous and ferric. The method demonstrated in this study provides a cost and time effective approach for the speciation of iron in ambient aerosols. - Highlights: • Dispersive absorption spectroscopic technique for trace level ferrous detection. • The spectral fitting retrieval improved the measurement precision and stability. • Extremely low detection limit was achieved for aqueous ferrous measurement. • Iron in size segregated particulate matters shows seasonal characteristic. • More active role of iron was found in fine particles compared to coarse particles.